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.     

混凝絮凝法去除腐质酸的研究

进行了混凝絮凝法去除水中腐殖酸的研究，结果表明，同传统的絮凝剂相比，微生物絮凝剂不仅用量少，去除效果好(去除率可达60％)，而且不产生二次污染，可应用于废水特别是给水中腐殖酸的去除工艺中，对絮凝剂的絮凝机理进行了初步研究，研究表明，微生物絮凝剂去除腐殖酸主要是通过架桥完成的，不同于A12(SO4)3的电中和机理。     

Enhanced bioaccumulation of cadmium in carp in the presence of titanium dioxide nanoparticles

In this study adsorption of Cd onto TiO2 nanoparticles and natural sediment particles (SP) were studied and the facilitated transports of Cd into carp by TiO2 nanoparticles and SP were assessed by bioaccumulation tests exposing carp (Cyprinus carpio) to Cd contaminated water in the presence of TiO2 and SP respectively. The results show that TiO2 nanoparticles had a significantly stronger adsorption capacity for Cd than SP. The presence of SP did not have significant influence on the accumulation of Cd in carp during the 25 d of exposure. However, the presence of TiO2 nanoparticles greatly enhanced the accumulation of Cd in carp. After 25 d of exposure Cd concentration in carp increased by 146%, and the value was 22.3 and 9.07 microg/g, respectively. And there is a positive correlation between Cd and TiO2 concentration. Considerable Cd and TiO2 accumulated in viscera and gills of the fish.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

腐殖酸、细颗粒泥沙对粉末活性炭吸附苯酚特性影响的研究

通过一系列实验,探讨了粉末活性炭吸附水中苯酚时,腐殖酸(HA)浓度和细颗粒泥沙用量对苯酚吸附量和去除率的影响.实验结果表明:在中性条件下,随着HA浓度的增加,粉末活性炭对苯酚的吸附量减少;在不同质量细颗粒泥沙的影响下,苯酚的去除率基本不变;在未加HA时,粉末活性炭对苯酚的吸附行为用Langmuir吸附等温式拟合效果最好,对苯酚的最大吸附量为150.60 mg/g,而在有HA存在时,粉末活性炭对苯酚的吸附行为用Freundlich吸附等温式拟合效果最好,对苯酚的最大吸附量为28.49 mg/g.     

Assessment of the physico-chemical behavior of titanium dioxide nanoparticles in aquatic environments using multi-dimensional parameter testing

Assessment of the behavior and fate of engineered nanoparticles (ENPs) in natural aquatic media is crucial for the identification of environmentally critical properties of the ENPs. Here we present a methodology for testing the dispersion stability, ζ-potential and particle size of engineered nanoparticles as a function of pH and water composition. The results obtained from already widely used titanium dioxide nanoparticles (Evonik P25 and Hombikat UV-100) serve as a proof-of-concept for the proposed testing scheme. In most cases the behavior of the particles in the tested settings follows the expectations derived from classical DLVO theory for metal oxide particles with variable charge and an isoelectric point at around pH 5, but deviations also occur. Regardless of a 5-fold difference in BET specific surface area particles composed of the same core material behave in an overall comparable manner. The presented methodology can act as a basis for the development of standardised methods for comparing the behavior of different nanoparticles within aquatic systems.     

用钛白废酸和副产锌泥制备活性氧化锌

以次硫酸氢钠甲醛副产锌泥和钛白废酸为原料,经高剪切乳化、酸浸、锌粉置换、除杂、碱锌合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备活性氧化锌。考察了浸取工艺液固比(硫酸与副产锌泥的质量比)和硫酸质量分数对锌浸出率的影响,以及煅烧温度和时间对活性氧化锌质量的影响。实验结果表明,锌泥酸浸工艺的最佳液固比4,硫酸质量分数30%,在此工艺条件下,锌浸出率达95%。活性氧化锌的最佳煅烧温度为600℃,煅烧时间为240 min,在此条件下测定产品质量,氧化锌质量分数大于96%,比表面积大于50 m2/g,堆积密度小于0.35 g/mL。     

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L⁻¹) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L⁻¹) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage.     

水环境中腐殖酸与镉离子结合作用的影响因素

通过测定不同化学条件下腐殖酸与镉离子作用后的游离态镉离子浓度及其结合率,研究各因素对腐殖酸与镉离子作用的影响。研究结果表明,pH值、离子强度、投加镉离子总浓度、腐殖酸浓度和反应温度均影响腐殖酸与镉离子的结合。pH值在4.5~6.5范围内,随pH值升高,腐殖酸与Cd²⁺的结合率增大,游离态Cd²⁺浓度减少。溶液的离子强度增大对结合反应有抑制作用。投加Cd²⁺总浓度的增大会导致结合态Cd²⁺浓度和游离态Cd²⁺浓度逐渐增加,而其结合率逐渐减小。腐殖酸浓度逐渐增大,使Cd²⁺和腐殖酸的结合率逐渐增大。在20℃~50℃范围内时,随反应温度升高,游离态Cd²⁺浓度逐渐减小,其结合率逐渐增加。     

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids

The competitive adsorption equilibrium isotherms of Cu²⁺ and Cd²⁺ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin–HA complex. This competitive adsorption shows that the presence of Cd²⁺ has not an important effect on Cu²⁺ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd²⁺ in the presence of Cu²⁺. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.     

The toxicity of titanium dioxide nanopowder to early life stages of the Japanese medaka (Oryzias latipes)

In this study, fertilized Japanese medaka (Oryzias latipes) embryos were exposed from fertilization to 5 d post-hatch using static non-renewal assays to aqueous suspensions of titanium dioxide nanoparticles (nTiO₂) ranging in nominal concentrations between 0 and 14 μg mL⁻¹. The average size of the nTiO₂ in the stock solution before addition to the test treatments was 87 nm (±14 nm). TiO₂ materials accumulated in a concentration dependent manner on the chorionic filaments of developing medaka embryos with evidence of pericardial edema occurring during embryo development. However, no significant (p > 0.05) increases in mortality relative to control treatments were observed for the nTiO₂ exposed embryos. A concentration dependent increase in cumulative percent hatch was observed at 11 d, indicating that exposure to increasing concentrations of nTiO₂ resulted in the premature hatch of medaka embryos. Post-hatch, a significant proportion of sac fry from the nTiO₂ exposure groups exhibited moribund swimming behavior and these individuals also experienced greater mortality at 15 d post-hatch. Combined, these results demonstrate that exposure to nTiO₂ can impact the development of early life stages of fish.     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

Role of magnetite and humic acid in radionuclide migration in the environment

Sorption of ¹³⁷Cs, ⁹⁰Sr, ¹⁵⁴Eu and ¹⁴¹Ce by magnetite has been studied at varying pH (4 to 11) in the presence and absence of humic acid. The sorption studies have also been carried out at varying ionic strength (0.01 to 0.2 M NaClO₄) and humic acid concentration (2 to 20 mg/L). Percentage sorption of ¹³⁷Cs and ⁹⁰Sr was found to be pH dependent, with the sorption increasing with increasing pH of the suspension. At any pH, the percentage sorption of ⁹⁰Sr was higher than that of ¹³⁷Cs. The results have been explained in terms of the electrostatic interaction between the positively charged metal ions and the surface charge of the magnetite which becomes increasingly negative with increasing pH. On the other hand, ¹⁵⁴Eu and ¹⁴¹Ce were found to be strongly sorbed by the magnetite at all pH values, with the sorption being independent of pH. The strong sorption of trivalent and tetravalent metal ions suggests the role of complexation reactions during sorption, apart from the electrostatic interactions. However, in the case of ¹⁴¹Ce surface precipitation of Ce(III) formed by reduction of Ce(IV) in the presence of magnetite cannot be ruled out. Presence of humic acid (2 mg/L) was found to have negligible effect on sorption of all metal ions.     

Atrazine biodegradation modulated by clays and clay/humic acid complexes

The fate of pesticides in the environment is strongly related to the soil sorption processes that control not only their transfer but also their bioavailability. Cationic (Ca-bentonite) and anionic (Layered Double Hydroxide) clays behave towards the ionisable pesticide atrazine (AT) sorption with opposite tendencies: a noticeable sorption capacity for the first whereas the highly hydrophilic LDH showed no interactions with AT. These clays were modified with different humic acid (HA) contents. HA sorbed on the clay surface and increased AT interactions. The sorption effect on AT biodegradation and on its metabolite formation was studied with Pseudomonas sp. ADP. The biodegradation rate was greatly modulated by the material's sorption capacity and was clearly limited by the desorption rate. More surprisingly, it increased dramatically with LDH. Adsorption of bacterial cells on clay particles facilitates the degradation of non-sorbed chemical, and should be considered for predicting pesticide fate in the environment.     

On the dissolution kinetics of humic acid particles. Effect of monocarboxylic acids

The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4–10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid < acetic acid < propionic acid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment.     

二氧化钛固定化负载及其光催化性能

利用溶胶-凝胶法及浸提技术,进行二氧化钛的固定化负载.通过XRD和SEM对其物相和微观形貌进行分析;利用甲基橙为目标污染物,探究制备以及催化工艺对二氧化钛催化降解性能的影响及其重复使用效果.结果表明,随着浸涂次数的增加,不锈钢丝网表面二氧化钛薄膜的微观形貌有所变化,对甲基橙的光催化降解效率呈现先增大后减少的趋势.浸提7次所制备的二氧化钛光催化降解效率最高,搅拌条件下的4h紫外光降解率可达77.6％.     

Sorption of thallium(I) onto geological materials: influence of pH and humic matter

The sorption behaviour of the severely toxic heavy metal thallium (Tl) as a monovalent cation onto three representative materials (goethite, pyrolusite and a natural sediment sampled from a field site) was examined as a function of pH in the absence and presence of two natural humic acids (HAs), using ²⁰⁴Tl(I) as a radiotracer. In order to obtain a basic understanding of trends in the pH dependence of Tl(I) sorption with and without HA, sorption of HAs and humate complexation of Tl(I) as a function of pH were investigated as well. In spite of the low complexation between Tl(I) and HAs, the presence of HAs results in obvious alterations of Tl(I) sorption onto pyrolusite and sediment. An influence on Tl(I) sorption onto goethite was not observed. Predictions of K_d (distribution coefficient) for Tl(I) on goethite in the presence of HAs, based on a linear additive model, agree well with the experimental data, while a notable disagreement occurs for the pyrolusite and sediment systems. Accordingly, it is suggested that HAs and goethite may act as a non-interacting sorbent mixture under the given conditions, but more complex interactions may take place between the HAs and the mineral phases of pyrolusite or sediment.