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.     

色谱、光谱及联用技术在多农药残留检测中的应用

介绍了国内外多农药残留检测的发展状况,综述了色谱法、光谱法、色谱-质谱联用技术、色谱-光谱联用法、多维气相色谱技术的特点及在多农药残留检测中的应用,指出多农药残留检测在今后的农药残留检测中将占据主导地位.     

电感耦合等离子体发射光谱法测定石化废水中的重金属

建立了硝酸加热消解后采用电感耦合等离子体发射光谱(ICP-OES)测定石化废水中重金属(As,Cd,Cr,Cu,Zn,Pb,Mn)的方法,优化了仪器工作参数,得到了线性回归方程,并对该方法进行了评价。优化后的仪器工作参数为射频功率1 150 W、雾化器流量0.70 L/min、辅助气流量0.50 L/min。各重金属元素回归方程的相关系数均在0.999 9以上,检出限为0.000 18~0.007 00 mg/L,相对标准偏差为0.1%~2.0%,加标回收率为96.3%~102.2%。该方法具有线性关系好、检出限低、精密度和准确度高、分析速度快等优点。     

Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PC_n, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg⁻¹ dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PC_n, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg ⁻¹ EDTA, vetiver accumulated 4460 and 480 mg Pb kg⁻¹ dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC₁) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC₁-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.     

Screening analysis of volatile organic contaminants in commercial inorganic coagulants used for drinking water treatment

A method for quality screening is suggested to detect volatile impurities in inorganic coagulants that are used for drinking water treatment. Static headspace gas chromatography with mass spectrometry detection (HS–GCMS) is sensitive and selective to detect volatiles in low concentrations. This study has discovered that volatile organic impurities are detectable in ferric and aluminium-based coagulants which are used for drinking water treatment. For ferric chloride, 2-propanol was detected at a level of 17–24 μg ml⁻¹, acetone at 0.7–1.7 μg ml⁻¹, 1,1,1-trichloroacetone at 0.02–0.04 μg ml⁻¹, trichloromethane at 0.01–0.02 μg ml⁻¹ and toluene at 0.01–0.12 μg ml⁻¹. For ferric chloride sulfate, acetone was detected at a level of 0.12 μg ml⁻¹, 1,1,1-trichloroacetone at 0.06–0.08 μg ml⁻¹, trichloromethane at 0.13–0.23 μg ml⁻¹, bromodichloromethane at 0.04–0.06 μg ml⁻¹ and dibromochloromethane at 0.04–0.05 μg ml⁻¹. For aluminium hydroxide chloride, only trichloromethane was detectable, but below the method detection limits (MDL). Although the concentrations of these impurities in commercial coagulants are low, this observation is important and should have impact on water industries for them to pay attention to the chemicals they are using for drinking water production.     

Spatial distribution of uranium and thorium in the surface soil around proposed uranium mining site at Lambapur and its vertical profile in the Nagarjuna Sagar Dam

The understanding and evaluation of the possible interactions of various naturally occurring radionuclides in the world's third largest man-made dam, Nagarjuna Sagar located in Andhra Pradesh, India and built on river Krishna assumed significance with the finding of uranium deposits in locations near the dam. For the present work, surface soil samples from the mineralized area of Lambapur, Mallapuram, Peddagattu and sediment core samples from the Nagarjuna Sagar dam were analyzed for naturally occurring radionuclides namely uranium and thorium using gamma spectrometric technique. Also toxic elements lead and chromium were analysed by the Energy Dispersive X-ray Fluorescence Spectrometer (EDXRF) technique. Surface soil samples show a variation from 25 to 291 Bq/kg (2.02–23.5 mg/kg) for ²³⁸U and 32–311 Bq/kg (7.9–76.9 mg/kg) for ²³²Th. U/Th concentration ratio in surface soil samples ranged from 0.19 to 0.31 and was found comparable with the nation wise average of 0.26. The study of sediment core samples reflected higher U/Th concentration ratio of 0.30–0.33 in the bottom section of the core as compared to 0.22–0.25 in the upper section. The concentration ratio in the upper section of the core was similar to the ratio 0.23 found in the western Deccan Basalt region through which the river originates. A higher concentration of lead and chromium was observed in the upper section of the core compared to bottom section indicating the impact of river input on the geochemical character of dam sediment.     

Origin and transport of U and Ra in riverine,estuarine and marine sediments of the Krka River,Croatia

Spatial distribution of ²³⁸U and ²²⁶Ra activities in sediment columns along the Krka River and estuary, were studied using gamma spectrometry. Markedly different ²³⁸U and ²²⁶Ra activities between riverine, estuarine and marine sediments were observed. Distribution of these radionuclides, as well as their anthropogenic and natural origin, was evaluated by activity measurements, taking into account sedimentation rates estimated by ¹³⁷Cs distribution in sediment columns.     

自动化前处理-气相色谱串联质谱法测定淡水鱼体中的有机磷阻燃剂

应用自动化前处理设备和气相色谱串联四级杆质谱仪建立了淡水鱼体中10种有机磷阻燃剂的检测方法。该方法先采用自动索氏提取仪进行样品的提取,再应用凝胶渗透色谱净化仪和florisil柱对提取液进行两级净化,最后用气相色谱串联四级杆质谱法(多反应监测模式)对样品中的有机磷阻燃剂(OPFRs)定性定量。实验表明,凝胶渗透色谱净化系统在以乙酸乙酯∶环己烷(1∶1,V/V)为流动相,流速为5.0 m L·min-1的条件下,收集OPFRs的最佳时间为900~1 680 s;方法的检出限为0.002~0.192 ng·g~(-1)湿重,加标水平为5.000 ng·g~(-1)湿重时,平均加标回收率为48.7%~122%,相对偏差除磷酸三乙酯(TEP)(17.7%)和磷酸三(1,3-二氯异丙基)酯(TDCP)(11.9%)外均小于10%。应用该方法测定采集于东江某污水处理厂入河排污口的鱼类样品时,回收率指示物(d27-TBP)的回收率为82.4%~114%,鱼类样品中∑OPFRs的浓度范围为nd~6.41 ng·g~(-1)湿重。     

Determination of Au(III) and Pd(II) ions by flame atomic absorption spectrometry in some environmental samples after solid phase extraction

A simple and sensitive solid phase extraction method was developed for simultaneous separation and preconcentration of gold and palladium ions with N-(4-methylphenyl)-2-{[(4-phenyl-5-pyridine-4-yl-4H-1,2,4-triazol-3-yl)thio]acetyl}hydrazine carbo thioamide complex on Amberlite XAD-1180 resin before their determination by flame atomic absorption spectrometry. Some analytical parameters such as HNO₃ concentration of the sample solution, amount of complexing agent, sample volume, eluent type and volume, effects of foreign ions and adsorption capacity of the resin were investigated for quantitative recovery of gold and palladium ions. The effects of some anions and cations were also examined. Under optimum conditions, the detection limits for gold and palladium ions were found to be 0.29 and 0.19 μg L^?1, respectively. The preconcentration factor for gold and palladium was 250. After being validated by standard addition and analysis of standard reference material, the procedure was successfully applied to the analysis of sea and stream water, anodic slime, gold ore, soil and electronic waste.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.