Sampling atmospheric pesticides with SPME: Laboratory developments and field study

To estimate the atmospheric exposure of the greenhouse workers to pesticides, solid phase microextraction (SPME) was used under non-equilibrium conditions. Using Fick's law of diffusion, the concentrations of pesticides in the greenhouse can be calculated using pre-determined sampling rates (SRs). Thus the sampling rates (SRs) of two modes of SPME in the lab and in the field were determined and compared. The SRs for six pesticides in the lab were 20.4-48.3 mL min⁻¹ for the exposed fiber and 0.166-0.929 mL min⁻¹ for the retracted fiber. In field sampling, two pesticides, dichlorvos and cyprodinil were detected with exposed SPME. SR with exposed SPME for dichlorvos in the field (32.4 mL min^-1) was consistent with that in the lab (34.5 mL min^-1). SR for dichlorvos in the field (32.4 mL min⁻¹) was consistent with that in the lab (34.5 mL min⁻¹). The trends of temporal concentration and the inhalation exposure were also obtained.     

微通道内细颗粒驻波会聚/分离过程的数值模拟

为了研究微通道内可吸入颗粒的声波会聚现象,在两相流的框架下,对三出口微通道颗粒分离元件实现了声-流场中的颗粒运动的两相流动计算;计算方法中,首次提出的颗粒方程全导数离散方法,并成功运用于两相流动颗粒轨道的计算;模拟结果表明了超声换能器的长度对颗粒会聚的影响和出口流量对颗粒分离的影响。计算结果为三出口微通道颗粒分离元件的设计和应用提供参考。     

Synthesis of novel polymer type sulfoxide solid phase combined with the porogen imprinting for enabling selective separation of polychlorinated biphenyls

We developed a novel polymer type sulfoxide-modified solid phase enabling to achieve selective separation of polychlorinated biphenyls (PCBs) from insulation oil. In this study, firstly we prepared base-polymer based on the concept of the molecular imprinting to capture PCBs in selectively, then, the sulfoxide groups were modified on the pore surface of base-polymers by changing preparation methods. As results of liquid chromatographic analyses for the polymers as columns, the base-polymer prepared by xylene as a porogenic solvent showed selective retention ability for chlorinated aromatic compounds by the porogen imprinting effect. Additionally, the polymer-type sulfoxide solid phases showed highly retention ability for PCBs by increasing amount of introduced sulfoxide groups. Consequently, the results of separation of PCBs comparing to insulation oil suggested that the prepared solid phase can be used for the selective separation of PCBs at the same level as a commercially available media utilized for the regulated method.     

Functional Relationships with N Deposition Differ According to Stand Maturity in Calluna-Dominated Heathland

Plant and soil bio(chemical) indicators are increasingly used to provide information on N deposition inputs and effects in a wide range of ecosystem types. However, many factors, including climate and site management history, have the potential to influence bioindicator relationships with N due to nutrient export and changing vegetation nutrient demands. We surveyed 33 heathlands in England, along a gradient of background N deposition (7.2–24.5 kg ha⁻¹ year⁻¹), using Calluna vulgaris growth phase as a proxy for time since last management. Our survey confirmed soil nutrient accumulation with increasing time since management. Foliar N and phosphorus (P) concentrations in pioneer- and mature-phase vegetation significantly increased with N deposition. Significant interactions between climate and N deposition were also evident with, for example, higher foliar P concentrations in pioneer-phase vegetation at sites with higher temperatures and N deposition rates. Although oxidized N appeared more significant than reduced N, overall there were more, stronger relationships with total N deposition; suggesting efforts to control all emissions of N (i.e., both oxidized and reduced forms) will have ecological benefits.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-014-0529-4) contains supplementary material, which is available to authorized users.     

Monitoring of Triazine and Phenylurea Herbicides in the Surface Waters of Greece

A large-scale study was implemented to monitor triazine and phenylurea herbicides in the main surface water bodies of continental Greece from October 1998 to September 1999. Samples from 10 rivers and 7 lakes were analyzed for the presence of five triazine (atrazine, cyanazine, prometryne, simazine, terbuthylazine) and five phenylurea (chlorotoluron, diuron, linuron, metobromuron, monolinuron) herbicides. The samples were extracted with C18 cartridges and analyzed by high-performance liquid chromatography–diode array detection (HPLC-DAD). The most frequently detected herbicides were atrazine, followed by prometryne, cyanazine, and simazine. The concentrations of the compounds were generally low (< 0.78 μ g/L) and are not considered harmful for the freshwater ecosystem. Most of the positive samples were taken from the water bodies of northern Greece where agricultural activity is more intense.     

利用铅锌尾矿和CRT玻璃固体废弃物协同制备微晶玻璃工艺

以铅锌尾矿和CRT玻璃固体废弃物为主要原料,采用烧结法制备微晶玻璃材料.为确定基础玻璃的成分,以及尾矿、CRT玻璃及各化工原料的用料比例,设计了正交实验;研究了CaO,Al2O3,MgO等氧化物添加量对微晶玻璃结构及性能的影响规律.通过差热分析（DTA）、X射线衍射（XRD）、扫描电镜（SEM）等分析方法,考察了微晶玻璃产品的晶相、晶体形貌特征及性能.结果表明：利用铅锌尾矿、CRT玻璃废弃物制备微晶玻璃的最佳配方为：尾矿20％、CRT玻璃30％、添加辅料石英砂29.7％、方解石25％、Al2O3 12％、晶核剂TiO2 1％.SEM和XRD分析可知,微晶玻璃的主晶相为透辉石;打磨抛光处理后,平均显微硬度为8.76 GPa,平均抗折强度为223.1MPa;经酸、碱浸蚀后,质量变化分别为0.43％和0.58％,耐酸碱腐蚀性良好.     

Selective separation of deltamethrin by molecularly imprinted polymers using a β-cyclodextrin derivative as the functional monomer

A deltamethrin-imprinted polymer (MIP₁) was prepared using bis(-6-O-butanediacid monoester)-β-cyclodextrin (BBA-β-CD) as the functional monomer and toluene 2,4-diisocyanate (TDI) as the cross-linker. In comparison to the molecularly imprinted polymer where β-CD was applied as the functional monomer (MIP₂), MIP₁ showed a higher specific binding capacity (ΔC_P) and an improved imprinting factor (IF) for deltamethrin. The selective recognition experiments demonstrated that compared to MIP₂, MIP₁ could better recognize its template over other substrates that had similar chemical structures. The solid phase extraction (SPE) of deltamethrin using MIP₁ as the adsorbent was further investigated. The recoveries of the molecularly imprinted solid phase extraction (MISPE) column for deltamethrin were 83.2–93.4% with relative standard deviations (RSD) of 2.03–6.19%. The method has been successfully applied to the enrichment of trace deltamethrin from real water samples.     

COMPARISON BETWEEN SOLID–PHASE EXTRACTION METHODS FOR THE CHROMATOGRAPHIC DETERMINATION OF ORGANOPHOSPHORUS PESTICIDES IN WATER

A solid-phase microextraction (SPME) procedure has been developed to ex tract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng.mL^?1 for SPE and 1 to 100 ng.mL^?1 for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng.mL^?1 for SPME depending upon the analyte, and 100 ng.mL^?1 for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6 % to 5.8 % for SPME and 2.4 % to 9.2 % for SPE.

Along with the feature of being a solvent – free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE – 500 mL, SPME – 5 mL).     

新型化粪池处理生活污水启动阶段的实验

在常温的条件下,用厌氧折流板反应器(ABR)化粪池、YDT填料化粪池和传统三格式化粪池处理生活污水,进行了对照实验研究。实验结果表明,在温度为14～29℃,HRT为36 h时,反应器运行85 d后,对以上3个反应器进出水中CODtot、CODdis、氨氮、总氮、总磷进行测定,在水温24℃稳定阶段,ABR化粪池和YDT填料化粪池CODtot去除率比传统化粪池分别提高30.5%和9.2%;在水温16℃稳定阶段时,该值分别提高10.9%和9.0%。总氮和氨氮去除率在5%～30%之间,稳定运行后总磷去除率为5%左右。通过测定3个反应器最后一格中厌氧污泥的比产甲烷速率,结果表明,ABR化粪池的厌氧污泥产甲烷的活性最好。此研究对传统化粪池的改造提出经济而行之有效办法,新型化粪池强化了化粪池出水的生化性和对污染物的去除,进而为化粪池的取舍和改造提供技术的参考依据。     

不同生育期美人蕉-微生物修复富营养化水体

生物修复水体富营养化,尤其是植物和微生物联合修复为目前水体富营养化治理方面的研究热点。不同生育期植物和微生物联合修复鲜见报道。研究不同生育期美人蕉和固定化微生物对富营养化水体的联合修复作用。结果表明,营养生长期和开花期美人蕉-微生物组处理前3天,富营养化水体中不同形态氮和磷浓度快速下降,用于美人蕉生长发育。从富营养化水体氮去除效果来看,营养生长期美人蕉-微生物联合处理去除效果略好于开花期,对磷的去除效果相反。美人蕉吸收氮元素为营养器官利用,其营养器官全氮增长量与生殖器官（花）形成显著差异（P<0.05）。花是美人蕉全磷含量最高、全磷增长量最高的器官,其全磷含量和全磷增长量与营养器官均形成显著差异（P<0.05）。实验结果表明,不同生育期美人蕉-微生物联合处理对氮和磷的吸收利用存在差异。