Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: Influence of acids on the photodegradation of gaseous toluene

In order to efficiently remove volatile organic compounds (VOCs) from indoor air, onedimensional titanate nanotubes (TiNTs) were hydrothermally treated to prepare TiO₂ nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH₃COOH, HNO₃, HCl, HF and H₂SO₄ used in the treatment were separately compared to optimize the performance of the TiO₂ nanocrystals. Comparedwith the strong and corrosive inorganic acids, CH₃COOH was not only safer andmore environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained TiO₂. Itwasobserved that the anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution exhibited the highest photodegradation rate of gaseous toluene (94%), exceeding that of P25 (44%) by a factor ofmore than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH₃COOH. The influence of relative humidity (20%-80%) on the performance of TiO₂ nanocrystals was also studied. The anatase TiO₂ synthesized in 15 mol/L CH₃COOH solution was more tolerant tomoisture than the other TiO₂ nanocrystals and P25.     

Surface modification of polypropylene non-woven fibers with TiO2 nanoparticles via layer-by-layer self assembly method: Preparation and photocatalytic activity

Polypropylene (PP) meltblown fibers were coated with titanium dioxide (TiO₂) nanoparticles using layer-by-layer (LbL) deposition technique. The fibers were first modified with 3 layers of poly(4-styrenesulfonic acid) (PSS) and poly(diallyl-dimethylammonium chloride) (PDADMAC) to improve the anchoring of the TiO₂ nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic TiO₂ nanoparticles to construct TiO₂/PDADMAC bilayer in the LbL fashion. The number of deposited TiO₂/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust TiO₂ loading. The LbL technique showed higher TiO₂ loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue (MB). Results showed that the TiO₂ modified fibers exhibited excellent photocatalytic activity efficiency similar to that of TiO₂ powder dispersed in solution. The deposition of TiO₂ 3 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr. TiO₂-LbL constructions also preserved TiO₂ adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of TiO₂ particles from the substrate outer surface. However, even in the third cycle, the TiO₂ modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.     

藏南羊卓雍错湖水化学空间分异特征

2010年7月对藏南羊卓雍错流域进行了水样采集,通过测定与分析,揭示了流域最大湖泊羊卓雍错表层湖水化学水平分布特征和深水剖面变化规律,并探讨了该湖与流域其他水体化学性质的差异。结果表明:流域特殊的高寒气候、湖泊形状与补给来源、湖岸水系发育程度不同是造成羊卓雍错湖水化学空间分异特征明显的关键。在水平方向上,湖水HCO3-、Ca2+以及矿化度南高北低,而SO42-和Mg2+南低北高。这是由于湖水从南向北缓慢流动过程中蒸发浓缩所致;卡鲁雄曲径流量经空姆错补给羊卓雍错北部,使其矿化度较低。在垂直方向上,愈向湖泊深处,湖水SO42-、Cl-、CO32-和矿化度愈大,HCO3-则降低。与流域其他湖泊相比,羊卓雍错水化学性质与同属以降水补给为主的湖泊相近,与以冰雪融水补给为主的湖泊差异显著。与河水和地下水相比,羊卓雍错湖水SO42-和Mg2+当量浓度最大,河水和地下水则HCO3-和Ca2+含量较大。     

鄂尔多斯盆地马家沟组马五_1亚段地层水特征及对CO_2地质封存的意义

CO_2地质封存技术是实现碳减排的有效措施,对鄂尔多斯盆地马家沟组马五_1亚段地层水特征进行研究,是下一步实施工程化CO_2封存的首要前提。本文依据对深部钻井取样的直观观察与实验测试,采用单项指标分类评价和多项指标综合评价的方法深入分析了马家沟组马五_1亚段地层水的物理性质、化学性质、地层水类型和水化学特征参数。结果表明:马家沟组马五_1亚段地层水密度较大、矿化度极高,属于卤水,含量最多的离子是Cl~-,其次是Ca~(2+),地层水是CaCl_2型。钠氯系数、氯镁系数、脱硫系数和镁钙系数的分析表明马五_1亚段地层水封闭性极好,处于较强的还原环境。综合分析认为马家沟组马五_1亚段地层水具备实施CO_2封存的良好条件,非常适宜进行CO_2封存。     

NITROGEN TRANSFORMATIONS IN SEDIMENTS AS AFFECTED BY CHEMICAL AMENDMENTS1

ABSTRACT: A study was conducted to elucidate some of the chemical factors affecting the rate and pathways of N transformations in lake sediments. The main emphasis was placed on modifying a noncalcareous sediment with CaCO₃ to approximate the composition of a calcareous sediment. Additionally, the effects of Ca²⁺, CO₃^2-, Mg2⁺ and OH^- were evaluated by using appropriate chemicals. Further, the effect of aluminum sulfate was evaluated with both sediment types. Sediment pH at 7 days was not affected by CaCO₃, but was decreased by aluminum sulfate. The CaCO₃ treatment increased the rate of ammonification, nitrification, reduction of acetylene to ethylene and methane formation, while with few exceptions the other treatments decreased the rate of the transformations studied. Aluminum sulfate, which has been proposed as a lake restoration treatment, increased ammonification but decreased most of the other transformations.     

Photocatalytic removal of nitrogen oxides via titanium dioxide

We studied the removal of nitrogen oxides pollutants via TiO₂ Degussa P25 powder by photocatalysis. Parameters such as mass of catalyst, geometric irradiated surface, catalyst morphology, and thermal treatment were tested to explain the photocatalytic concentration decrease of nitrogen oxides. According to our working conditions, the conversion rates increased until an optimal value of the TiO₂ weight, 35% of NO concentration and around 20% of NOx, was decomposed by the photocatalysis. The NOx removal increased proportionally with the irradiated geometric surface. The structural transformation of anatase to rutile performed by thermal treatment involved the decrease of the photocatalytic activity.     

Nitrogen availability in relation to vegetation changes resulting from grass encroachment in Dutch dry dunes

The encroachment of some tall grass species in open dune vegetation, as observed in a Dutch dry dune area, is considered unfavourable from a conservation viewpoint. This paper investigates differences in vegetation and soil properties between grass-dominated and still existing open dune grassland plots at four locations along the coast. Soil properties studied include nitrogen and phosphorus pools and nitrogen availability by mineralization. Vegetation properties included are above and below-ground biomass and nitrogen and phosphorus concentrations in above-ground biomass. Systematic differences in N-pools between grass-dominated and open dune grassland plots were not observed. However, N-availability by mineralization and its turnover rates are higher in grass-dominated plots than in open dune grassland plots, as well as above and below-ground biomass. In open dune grassland plots, atmospheric N-input is an important source of N, whereas in grass-dominated plots mineralization largely exceeds atmospheric N-input. However, these observations do not explain the mosaic-like vegetation pattern. Grazing intensity is most likely the determinant factor in the dry dune system. It is concluded, that grass encroachment is probably triggered by atmospheric deposition and is enhanced by positive feedbacks in the N-cycle. The relevance of these results for restoration management is briefly discussed.     

二氧化钛纳米颗粒对湖滨沼泽土壤氮矿化的影响

二氧化钛纳米颗粒（TiO₂NPs）的广泛应用使其环境释放量不断增加,从而影响到土壤氮的转化过程.然而,目前关于TiO₂NPs对湖滨沼泽土壤氮矿化的影响机制尚不明确.因此,本研究以典型沼泽土壤为研究对象,通过室内培养实验研究不同剂量TiO₂NPs处理（0 mg·kg^-1（CK）、10 mg·kg^-1（A10）、100 mg·kg^-1（A100）、250 mg·kg^-1（A250）、1000 mg·kg^-1（A1000））对土壤理化性质、酶活性和氮矿化过程的影响,探讨TiO₂NPs输入对土壤氮矿化过程影响的内在机制.结果表明：①不同剂量TiO₂NPs处理显著降低了土壤pH和总有机碳（TOC）含量（p<0.05）,A100、A250和A1000处理显著降低了硝态氮（NO₃^--N）含量（p<0.05）.②A250和A1000处理显著抑制了过氧化氢酶活性（p<0.05）;培养7 d,不同剂量TiO₂NPs处理均显著促进了脲酶活性（p<0.05）,抑制了脱氢酶活性（p<0.05）;随着培养时间延长,TiO₂NPs处理对脲酶和脱氢酶活性的抑制作用逐渐减弱,表明TiO₂NPs的负面作用会随时间减弱.③不同剂量TiO₂NPs处理对氨化速率没有显著影响（p>0.05）,A250、A1000处理对硝化和矿化速率有显著抑制作用（p<0.01）.④土壤氮矿化速率与土壤pH、总磷（TP）、NO₃^--N含量呈显著正相关,与脲酶、过氧化氢酶活性呈显著负相关.TiO₂NPs主要通过改变沼泽土壤NO₃^--N含量影响氮矿化过程.本研究可为湖滨湿地保护和TiO₂NPs环境风险评估提供理论依据.