Freeze-induced acceleration of iodide oxidation and consequent iodination of dissolved organic matter to form organoiodine compounds

Freeze-induced acceleration of I-oxidation and the consequent iodination of dissolved or-ganic matter(DOM)contribute to the formation of organoiodine compounds(OICs)in cold regions.The formed OICs may be a potentially important source of risk and are very closely with the environment and human health.Herein,we investigated the acceleration effects of the freeze process on I-oxidation and the formation of OICs.In comparison to reac-tive iodine species(RIS)formed in aqueous solutions,I-oxidation and RIS formation were greatly enhanced in frozen solution and were affected by pH,and the content of I-and O2.Freeze-thaw process further promoted I-oxidation and the concentration of RIS reached 45.7 μmol/L after 6 freeze-thaw cycles.The consequent products of DOM iodination were greatly promoted in terms of both concentration and number.The total content of OICs ranged from 0.02 to 2.83 μmol/L under various conditions.About 183-1197 OICs were de-tected by Fourier transform ion cyclotron resonance mass spectrometry,and more than 96.2％ contained one or two iodine atoms.Most OICs had aromatic structures and were formed via substitution and addition reactions.Our findings reveal an important forma-tion pathway for OICs and shed light on the biogeochemical cycling of iodine in the natural aquatic environment.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

玻璃注射器对顶空气相色谱法分析苯系物的误差原因分析

按GB11890—89顶空气相色谱法分析苯系物时，发现重复性和分割水平样品平行性较差，经仔细分析，是由于使用普通玻璃注射器造成的。为避免此类误差，建议顶空气相色谱法分析时，使用带特氟龙顶端推杆的气密性注射器。     

Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

宁波市大气可吸入颗粒物PM1o和PM2.5的源解析研究

在宁波市布设4个代表性点位,于2010年春季、夏季和冬季进行大气PM10和PM2.s的采样,同时采集了多种颗粒物源样品,建立了PM10、PM2.5和源样品的化学成分谱.采用化学质量平衡模型(CMB)对宁波市PM10、PM2.5进行源解析.结果表明,城市扬尘、煤烟尘、机动车尾气尘是宁波市PM10、PM2.5的3大污染源,...     

The dissipation rates of trichlorfon and its degradation product dichlorvos in cabbage and soil

The residual levels and dissipation rate of trichlorfon, and its degradation product, dichlorvos, in cabbage crops and the soil in which these were grown, were determined by gas chromatography at two geographically distant experimental sites, one in Kunming and one in Beijing, China. Trichlorfon was applied at two dosages (900 g ai ha⁻¹ and 1350 g ai ha⁻¹). Maximum final residues of trichlorfon in soil and cabbage were 1.23 mg kg⁻¹ and 1.81 mg kg⁻¹ respectively at Kunming, and 0.35 mg kg⁻¹ and 0.70 mg kg⁻¹ respectively at Beijing. However, the final residues of dichlorvos in both cabbage and soil was only 0.04 mg kg⁻¹ at Kunming, and only 0.03 mg kg⁻¹, or “not detectable”, at Beijing. The mean half-life of trichlorfon in cabbage was 1.80 d with a dissipation rate of 90% over 5 d, while that in soil was 3.05 d with a dissipation rate of 90% over 14 d at one experimental site. The dissipation rates of trichlorfon and its degradation product dichlorvos at the two experimental sites were different, suggesting that degradation of these pesticides was affected by local soil characteristics and climate. When applied at both the recommended dosage and at 1.5 times this, no detectable residues of either trichlorfon or dichlorvos were found in soil or cabbage at harvest. Although trichlorfon can easily degrade into dichlorvos, which is highly toxic to humans and other animals, the observed low residual levels of dichlorvos suggest that trichlorfon is safe when applied at the recommended dosage.     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

磺胺类制药废水中苯系物的快速同步检测

磺胺类制药废水是一类难降解有机废水,其中含有苯磺酰胺、苯磺酸、苯酚等苯系物,对这些物质的快速检测十分必要,针对这3种物质建立了基于高效液相色谱的快速同步检测方法。采用C₁₈柱为分离柱,比较了乙腈/水、甲醇/水和甲醇/缓冲盐3种流动相体系的分离效果,优化了230、240、250和260 nm 4种检测波长等条件。结果表明,V_甲醇∶V_{磷酸二氢铵溶液}(0.5%,pH=3.5)=50∶50作为流动相时,基线稳定,峰形较好,3种目标物在11 min内即可实现有效分离,且浓度为5~100 mg·L⁻¹时,3种目标物峰面积与质量浓度的线性关系良好(R²>0.999),检出限为15.0~29.4 μg·L⁻¹,相对偏差为0.05%~1.56%(n=5),该方法能同时检测苯磺酸、苯酚和苯磺酰胺,具有简便、灵敏、准确等优点,可为制药废水的快速检测和磺胺类药物降解机理的分析提供便利。     

Analysis of metabolic changes in Trichoderma asperellum TJ01 at different fermentation time-points by LC-QQQ-MS

Trichoderma spp. are among the most widely recognized biocontrol fungi used to inhibit pathogens and promote plant growth. These functions are related to primary and secondary metabolites. This study investigated the different metabolites in Trichoderma asperellum TJ01 cultured for 24 and 72?h using liquid chromatography with triple-quadrupole mass spectrometry. Compared to the 24?h culture of T. asperellum TJ01, the 72?h culture with amino acid metabolism tended to decrease while sugar and lipid metabolisms tended to increase. Furthermore, the 72?h culture had a higher proportion of upregulated flavonoids, in combination with a higher proportion of downregulated alkaloids, and equal proportions of upregulated and downregulated polyphenols and hormones. This study also identified a few valuable medicinal substances such as trigonelline and 5-hydroxytryptophan in T. asperellum TJ01 fermentation cultures.