Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

Comparison of manufactured and black carbon nanoparticle concentrations in aquatic sediments

In this paper, we show that concentrations of manufactured carbon-based nanoparticles (MCNPs) in aquatic sediments will be negligible compared to levels of black carbon nanoparticles (BCNPs). This is concluded from model calculations accounting for MCNP sedimentation fluxes, removal rates due to aggregation or degradation, and MCNP burial in deeper sediment layers. The resultant steady state MCNP levels are compared with BCNP levels calculated from soot levels in sediments and weight fractions of nanosized fractions of these soot particles. MCNP/BCNP ratios range from 10⁻⁷ to 10⁻⁴ (w:w). This suggests that the often acclaimed effect of MCNPs on organic pollutant binding and bioavailability will likely be below the level of detection if natural BCNPs are present, even if binding to MCNP is one to two orders of magnitude stronger than to BCNPs. Furthermore, exposure and toxic effects of MCNPs in sediments and soils will be negligible compared to that of BCNPs.     

铂载钴钼二元硫化物对H_2S电催化活性研究

为考察溶胶凝胶法制备的Co-Mo二元硫化物对H_2S气体的电催化活性,通过循环伏安法和Tafel曲线分析对铂载不同Co、Mo掺杂比的电催化剂进行表征.结果表明,不同阳极电催化剂交换电流密度J_0由大到小依次为,铂载n(Co):n(Mo)=2:3、铂载n(Co):n(Mo)=2:1、铂载n(Co):n(Mo)=1:1和铂,即铂载n(Co):n(Mo)=2:3阳极电催化剂具有较好的活性,这与循环伏安曲线测试结果一致.电解质溶液pH值为6～7时,随着温度的升高铂载n(co):n(Mo)=2:3阳极电催化剂活性呈现上升的趋势.优化后的Co、Mo掺杂原子比约为0.66,此类电催化剂在操作温度80℃下,交换电流密度为1.318mA/cm~2,表观活化焙值为616.6 kJ/mol .研究表明,铂载钴钼二元硫化物适合作为低温H_2S燃料电池阳极电催化剂,其中Co、Mo掺杂比对电催化活性影响较大.     

高气速间歇式生物过滤去除高负荷H2S

采用生物过滤法,以鸡粪堆肥和PE混合物为填料,在高气速条件下间歇式处理高负荷H2S废气。空床停留时间为20、15、10、6.7和5 s时,入口浓度3 000 mg/m3下的平均去除率分别为100%、100%、96.5%、89.2%和90.5%。高气速EBRT为5 s时,高入口负荷2 147 g/(m3.h)时的去除负荷为2 023 g/(m3.h),去除率达94%。采用Michaelis-Ment-en模型进行生物降解宏观动力学研究,其中Ks为550 mg/m3,Vm为6.8×104g/(m3.d)。结果表明,在实验温度17～24℃,湿度30%～50%下,生物过滤法间歇式处理高气速高负荷H2S的去除性能好。     

The silvering process of European eel (Anguilla anguilla) influences PAH metabolite concentrations in bile fluid: consequences for monitoring

The stock of the catadromous European eel (Anguilla anguilla L.) continues to decline and there is growing evidence that poor health status due to contaminants might be a key element in this decrease. Organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) belong to the major threats to yellow eel in their growth habitat and their metabolites are detectable in the bile. Starting the silvering process eels undergo physiological and morphological changes including cessation of feeding and downstream migration back to their spawning grounds. Reduced feed intake results in a diminishment of bile production and induces accumulation of e.g. PAH-metabolites in bile. Therefore, the aim of the present study was to demonstrate the impact of silvering on biliary PAH metabolite concentrations and to utilize normalization procedures to overcome silvering related accumulation effects of PAH-metabolites in eel bile. We investigated the hydroxyl-metabolites of pyrene (1-OH Pyr) and phenantrene (1-OH Phen) in the bile of different maturation stages of eels (silvering index I-V) from nine German rivers. We detected increasing absolute PAH metabolite levels in bile during the silvering process. The highest rise could be observed at the transition from pre migration stage III to the migrating stage IV, suggesting the onset of cessation of feeding at this stage. A cessation bias in PAH metabolite measurement could be diminished by normalization of absolute values against bile pigments (A₃₈₀, biliverdin). In conclusion, we demonstrated the impact of silvering on PAH metabolite concentrations in eel bile and present suitable normalization procedures to overcome silvering related accumulation effects. Thus, for a future eel monitoring we recommend (1) to regularly monitor PAH metabolites in bile, (2) to determine silvering index of eel and (3) to normalize PAH metabolite values in bile based on maturation/silvering stages. The knowledge of the silvering stage is mandatory for an unbiased evaluation of PAH contamination of European eel towards an international harmonized eel monitoring program.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Distribution and bioavailability of ceria nanoparticles in an aquatic ecosystem model

Along with the increasing utilization of engineered nanoparticles, there is a growing concern for the potential environmental and health effects of exposure to these newly designed materials. Understanding the behavior of nanoparticles in the environment is a basic need. The present study aims to investigate the distribution and fate of ceria nanoparticles in an aquatic system model which consists of sediments, water, hornworts, fish and snails, using a radiotracer technique. Concentrations of ceria in the samples at regular time intervals were measured. Ceria nanoparticles were readily removed from the water column and partitioned between different organisms. Both snail and fish have fast absorption and clearance abilities. Hornwort has the highest bioaccumulation factors. At the end of the experiment, sediments accumulated most of the nanoparticles with a recovery of 75.7 ± 27.3% of total ceria nanoparticles, suggesting that sediments are major sinks of ceria nanoparticles.     

不同粒径零价铁（ZVI）对污水污泥H_2S和CH_4释放速率的影响

考察了不同粒径零价铁（ZVI）,包括200目普通铁粉（200m-ZVI）、800目超细铁粉（800m-ZVI）和纳米铁粉（nZVI,粒径=20 nm）,对污水污泥的硫化氢和甲烷释放速率的影响。研究发现：（1）在22 d内,添加0.1%的200m-ZVI使污泥的硫化氢释放速率提高48.0%,而添加0.1%的800-ZVI和nZVI,则使污泥的硫化氢释放速率分别降低33.1%和77.1%;（2）不同粒径ZVI均可以提高污泥沼气中的甲烷浓度,且依次为nZVI〉800m-ZVI〉200m-ZVI;（3）在23 d内,添加0.1%的200m-ZVI和nZVI使污泥的甲烷累计产生量分别提高了15.5%和40.6%,而添加0.1%800m-ZVI则使甲烷产生量降低了12.5%。nZVI可以有效控制污泥的硫化氢释放,并显著提升污泥在厌氧发酵过程的产甲烷速率。     

Hydrogen Sulfide Gas Treatment by a Chemical‐Biological Process: Chemical Absorption and Biological Oxidation Steps

In order to remove high concentrations of hydrogen sulfide (H₂S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H₂S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H₂S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe^2 + concentrations, pH, and glucose concentrations on Fe^2 + oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H₂S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass‐transfer was verified as the rate‐determining step in the chemical reaction through model validation. The Fe^2 + production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35°C in which more than 90% Fe^3 + formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe^2 + oxidation and the growth of T. ferrooxidans CP9.