Ozone-driven photocatalyzed degradation and mineralization of pesticide,Triclopyr by Au/TiO2

Triclopyr is a widely used pesticide which is non-biodegradable and enters aquatic systems. The ozone facilitated photocatalyzed degradation and mineralization of Triclopyr using Au-loaded titania as heterogeneous catalyst is reported. The oxidative degradation activity of the hazardous pesticide was investigated at pH 7.8 under varied reaction conditions, including in presence and absence of ozone, titania alone, in presence and absence of light and with different loadings of Au on support. Photocatalysis with 2% Au/TiO₂ in the presence of ozone yielded 100% degradation of Triclopyr in 2 h. The extent of degradation of pesticide and its mineralization were confirmed by GC-MS. For 10 mg/L of Triclopyr, 0.1 g/L of catalyst was found to be the optimum for mineralization. Results show that photocatalyzed ozonation with Au/TiO₂ as catalyst is a very effective for its removal. No leaching of Au was observed in triplicate runs. Catalyst was fully recoverable and reusable with no loss of activity.     

Nitrogen Budget of a Spruce Forest Ecosystem After Six-year Addition of Ammonium Sulphate in Southwest Sweden

A nitrogen (N) budget was constructed for a period of 6 years (1988–1993) in a Norway spruce stand with current deposition of 19 kg N and 22 kg S ha⁻¹ year⁻¹. The stand was fertilized annually by addition of 100 kg N and 114 kg S ha⁻¹ (NS). Above and below ground biomass, litterfall, fine- root litter production, soil solution and net mineralization were measured to estimate pools, fluxes and accumulation of nitrogen. The average needle litterfall in control (C) and NS plots in 1993 was 2.2 and 2.5 ton ha⁻¹ year⁻¹, respectively. The fine root litter production prior to treatment (1987) was 4.4 ton ha⁻¹ year⁻¹ and after treatment (1993) it was 4.5 and 3.9 ton ha⁻¹ year⁻¹ in C and NS plots, respectively. Net N mineralization in the soil profile down to 50 cm was estimated to be 86 and 115 kg ha⁻¹ year⁻¹ in C and NS plots, respectively in 1992. During the treatment period the uptake of N in the needle biomass in C and NS plots was 29 and 77 kg ha⁻¹ year⁻¹, respectively. No N was accumulated in needles of C plot where the NS plots accumulated 34 kg ha⁻¹ year⁻¹. Of the annually added inorganic N to NS plots 47% was accumulated in the above and below ground biomass and 37% in the soil. N fluxes via fine-root litter production in the C plots were much higher (54 kg ha⁻¹ year⁻¹) than that via litterfall (29 kg ha⁻¹ year⁻¹). The corresponding values in the NS plots were 65 and 43 kg ha⁻¹ year⁻¹, respectively. Most of the net N mineralization occurred in the FH layer and upper mineral soil. It is concluded that fine root litter and litterfall play an important role in the cycling of N. Despite a high N uptake the losses of N in litterfall and fine root litter resulted in an incorporation of N in soil organic matter.     

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).     

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.     

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.     

钙法解吸并固定乙醇胺富液中CO2

针对醇胺类吸收剂富液中CO_2的解吸及后续处置所存在的不足,提出一种新型解吸方案——钙法.通过CO_2负荷试验和Ca(OH)_2投加量试验确定了该法理想处理负荷为0.84 mol·L-1,理想投加比例为C∶Ca=1∶1(摩尔比),此条件下反应15 min和30 min的解吸率达到52.17%和55.02%,这表明钙法矿化解吸乙醇胺富液中CO_2是可行的.在此基础上,进一步研究了pH、温度和搅拌强度对CO_2解吸固定效果的影响.试验结果表明,CO_2解吸率随着pH和搅拌强度的增加而增大,但当pH和搅拌强度增大到一定程度后,解吸率增长放缓甚至出现下降.较高的解吸温度尽管解吸率更大,但高温条件下无法达到矿化固定CO_2的目的.CO_2二次吸收负荷试验表明经钙法解吸后的MEA再生液具有良好的可重复使用性.     

洱海流域农田土壤氮素的矿化及其影响因素

采用好氧间歇淋洗培养法,对洱海流域内的农田、菜地土壤样品培养2周,研究土壤氮的矿化及其影响因素.结果表明,表层土壤2周氮矿化量平均为65.54mg/kg.不同农田利用方式下,表层土壤氮矿化量的平均值为露地菜田粮田大蒜田.土壤氮素矿化以硝态氮为主,且随着土壤深度的增加而降低.土壤氮矿化同全氮、有机质含量呈明显的正相关关系,与pH值呈负相关;氮矿化与无机氮含量、C/N之间无显著关系.全氮、有机质和pH值是影响该流域农田土壤矿化的主要因子.