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.     

Carbon dioxide emissions from cities in China based on high resolution emission gridded data

Based on the China high resolution emission gridded data (1 km spatial resolution), this article is aimed to create a Chinese city carbon dioxide (CO₂) emission data set using consolidated data sources as well as normalized and standardized data processing methods. Standard methods were used to calculate city CO₂ emissions, including scope 1 and scope 2. Cities with higher CO₂ emissions are mostly in north, northeast, and eastern coastal areas. Cities with lower CO₂ emissions are in the western region. Cites with higher CO₂ emissions are clustered in the Jing-Jin-Ji Region (such as Beijing, Tianjin, and Tangshan), and the Yangtze River Delta region (such as Shanghai and Suzhou). The city per capita CO₂ emission is larger in the north than the south. There are obvious aggregations of cities with high per capita CO₂ emission in the north. Four cities among the top 10 per capita emissions (Erdos, Wuhai, Shizuishan, and Yinchuan) cluster in the main coal production areas of northern China. This indicates the significant impact of coal resources endowment on city industry and CO₂ emissions. The majority (77%) of cities have annual CO₂ emissions below 50 million tons. The mean annual emission, among all cities, is 37 million tons. Emissions from service-based cities, which include the smallest number of cities, are the highest. Industrial cities are the largest category and the emission distribution from these cities is close to the normal distribution. Emissions and degree of dispersion, in the other cities (excluding industrial cities and service-based cities), are in the lowest level. Per capita CO₂ emissions in these cities are generally below 20 t/person (89%) with a mean value of 11 t/person. The distribution interval of per capita CO₂ emission within industrial cities is the largest among the three city categories. This indicates greater differences among per capita CO₂ emissions of industrial cities. The distribution interval of per capita CO₂ emission of other cities is the lowest, indicating smaller differences of per capita CO₂ emissions among this city category. Three policy suggestions are proposed: first, city CO₂ emission inventory data in China should be increased, especially for prefecture level cities. Second, city responsibility for emission reduction, and partitioning the national goal should be established, using a bottom-up approach based on specific CO₂ emission levels and potential for emission reductions in each city. Third, comparative and benchmarking research on city CO₂ emissions should be conducted, and a Top Runner system of city CO₂ emission reduction should be established.     

北京市某高层建筑高空电磁辐射环境影响分析

选取北京市某代表性高层居民楼顶平台作为高空电磁辐射环境水平监测点进行综合场强和选频监测，评价总体电磁辐射环境水平，并分析监测区域电磁辐射能量的来源。结果表明：该高空监测区域的电磁辐射环境总体水平低于国家规定的公众照射导出限值，但高于地面水平。监测区域主要受30 km 外的中波台影响，其次是9 km 外的中央电视塔。影响最大的是639 kHz频率的中波信号，占100 kHz～300 MHz总场强的95％以上，其次是1．28 MHz频率的中波信号。提出，开展敏感建筑物规划建设时，应考虑中波的传播特性和对环境的影响。     

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。     

气相分子吸收光谱法测定地表水中硫化物

采用气相分子吸收光谱法测定地表水中硫化物,方法检出限为0.002 mg/L,水样加标回收率为96.5%~107%,精密度(RSD,n=6)为0.08%~1.38%。实验结果表明:该方法准确可靠、灵敏度好、操作简便,适用于地表水中硫化物分析要求。     

石墨炉原子吸收法测定水中铊的方法改进

采用石墨炉原子吸收法测定水中铊，对样品前处理的多个细节进行改进，使前处理过程耗时缩短，回收率提高。试验表明，方法在0μg/L ～50．0μg/L范围内线性良好，相关系数r为0．9995；检出限为2．0μg/L，取样量为500 mL，富集50倍时，方法检出限为0．04μg/L；实际水样测定结果的 RSD 为4．9％～8．4％；实际样品的加标回收率为94．0％～102％。     

气相色谱-高分辨双聚焦磁质谱测定水中超痕量多氯萘

采用固相萃取法处理水样，气相色谱-高分辨双聚焦磁质谱法测定水中超痕量多氯萘，同位素内标法定量，并对样品前处理条件和仪器条件进行优化。试验表明：方法在0．500 ng/L～500 ng/L范围内线性良好；当取样体积为1 L时，方法检出限为0．005 ng/L～0．01 ng/L；对实际水样进行2个质量浓度水平的加标回收试验，平行测定6次的 RSD为2．7％～8．7％，回收率为70．2％～110％。方法适用性试验表明，水样中复杂的基质对测定无影响。     

高氯低COD值水样的无汞快速测定法

以硝酸银和硫酸铬钾代替硫酸汞来消除 COD 测定中的氯离子干扰，同时将重铬酸钾溶液的浓度降低为0.100 mol／L，并用硫磷混酸代替硫酸，该方法经过对标准样品和实际样品的测定，表现出对于测定氯离子含量低于25000 mg／L的高氯低 COD 值水样具有较好的准确度和精密度，同时可以实现银盐的回收再利用。     

Development of heat transfer and evaporation model of LNG covered by Hi-Ex foam

Natural gas is a kind of clean, efficient green energy source, which is used widely. Liquefied natural gas (LNG) is produced by cooling natural gas to −161 °C, at which it becomes the liquid. Once LNG was released, fire or explosion would happen when ignition source existed nearby. The high expansion foam (Hi-Ex foam) is believed to quickly blanket on the top of LNG spillage pool and warm the LNG vapor to lower the vapor cloud density at the ground level and raising vapor buoyancy. To identify the physical structure after it contacted with LN₂ and to develop heat transfer model, the small-scale field test with liquid nitrogen (LN₂) was designed. In experiment, three layers including frozen ice layer, frozen Hi-Ex layer and soft layer of Hi-Ex foam were observed at the steady state. By characterizing physical structure of the foam, formulas for calculating the surface of single foam bubble and counting foam film thickness were deduced. The micro heat transfer and evaporation model between cryogenic liquid and Hi-Ex foam was established. Indicating the physical structure of the frozen ice layer, there were a certain number of icicles below it. The heat transfer and evaporation mathematical model between the frozen ice layer and LNG was derived. Combining models above with the heat transfer between LNG, ground and cofferdam, the heat transfer and evaporation mathematical model of LNG covered by Hi-Ex foam was developed eventually. Finally, LN₂ evaporation rate calculated by this model was compared with the measured evaporation rate. The calculated results are 1.2–2.1 times of experimental results, which were acceptable in engineering and proved the model was reliable.     

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.