Protonated acetone ion chemical ionization time-of-flight mass spectrometry for real-time measurement of atmospheric ammonia

Ammonia (NH₃) is ubiquitous in the atmosphere, it can affect the formation of secondary aerosols and particulate matter, and cause soil eutrophication through sedimentation. Currently, the use of radioactive primary reagent ion source and the humidity interference on the sensitivity and stability are the two major issues faced by chemical ionization mass spectrometer (CIMS) in the analysis of atmospheric ammonia. In this work, a vacuum ultraviolet (VUV) Kr lamp was used to replace the radioactive source, and acetone was ionized under atmospheric pressure to obtain protonated acetone reagent ions to ionize ammonia. The ionization source is designed as a separated three-zone structure, and even 90 vol.% high-humidity samples can still be directly analyzed with a sensitivity of sub-ppbv. A signal normalization processing method was designed, and with this new method, the quantitative relative standard deviation (RSD) of the instrument was decreased from 17.5% to 9.1%, and the coefficient of determination was increased from 0.8340 to 0.9856. The humidity correction parameters of the instrument were calculated from different humidity, and the ammonia concentrations obtained under different humidity were converted to its concentration under zero humidity condition with these correction parameters. The analytical time for a single sample is only 60 sec, and the limit of detection (LOD) was 8.59 pptv (signal-to-noise ratio S/N = 3). The ambient measurement made in Qingdao, China, in January 2021 with this newly designed CIMS, showed that the concentration of ammonia ranged from 1 to 130 ppbv.     

Research on distribution performance of desert sand for heat storage in downcomer

In this research, desert sand is used as the sensible heat storage medium, which exchanges heat with air in the downcomer to realize heat storage and heat release. The desert sand distribution uniformity has a significant impact on the heat exchange performance and efficiency between desert sand and air for the process of convection in the downcomer. Given the superiority of sensible heat storage in convective heat transfer between desert sand and air, distributors with cylinder or conical bore solid particles and homogeneity performance testing device are designed and manufactured on the basis of convection system equipped with solid particle–air downcomer. Then, the convection experiment between solid sand and air is researched. The greater the desert sand flow rate and higher the volume density, the larger the variance of regional mass flow rate and the worse the homogeneity performance. For the cylinder bore distributor, the smaller the sand particle size is, the greater affected the sand groups can be. The sand homogeneity performance is preferable with the two particle size ranges: 0.18-0.25 mm and 0.15-0.18 mm. The total sand flow rate decreases, but the uniformity improves with the increase of the air flow velocity, and the best distribution performance is achieved at an air velocity of 0.6 m/s. However, the distribution performance declines with the air flow velocity persistently increasing because the sand groups are pushed to one pipe side close to the wall. The sand groups deflect seriously with the air flow velocity increasing.     

苏州城区能见度与颗粒物浓度和气象要素的相关分析

利用苏州市2009年9月─2010年5月的颗粒物(包括黑碳,PM_2.5和PM₁₀)质量浓度、能见度、相对湿度、风速、风向、气温等观测资料,分析了苏州城区能见度与颗粒物质量浓度及气象要素的相关关系.结果表明:ρ(黑碳),ρ(PM_2.5)和ρ(PM₁₀₎与能见度的r(相关系数)分别为-0.465,-0.359和-0.238,这3种颗粒物中,能见度与ρ(黑碳)的相关性最显著.当相对湿度≤60%时,ρ(黑碳),ρ(PM_2.5)和ρ(PM₁₀₎与能见度的r分别为-0.675,-0.411和-0.364.相对湿度较低时,颗粒物与能见度相关性较好.能见度与温度、风速的r分别为0.132和0.188,与相对湿度的r为-0.632.用颗粒物质量浓度和气象要素建立的能见度多元线性回归模型效果不好,在该模型基础上用ρ(黑碳),ρ(PM₁₀₎和相对湿度建立了能见度的多元二次回归模型,R(复相关系数)达到0.865,R2(复决定系数)达到0.749.      

Integrated modelling of foraging behaviour, energy budget and memory properties

A predator's foraging performance is related to its ability to acquire sufficient information on environmental profitability. This process can be affected by the patchy distribution and clustering of food resources and by the food intake process dynamics.We simulated body mass growth and behaviour in a forager acting in a patchy environment with patchy distribution of both prey abundance and body mass by an individual-based model. In our model, food intake was a discrete and stochastic process and leaving decision was based on the estimate of net energy gain and searching time during their foraging activities. The study aimed to investigate the effects of learning processes and food resource exploitation on body mass and survival of foragers under different scenarios of intra-patch resource distribution.The simulation output showed that different sources of resource variability between patches affected foraging efficiency differently. When prey abundance varied across patches, the predator stayed longer in poorest patches to obtain the information needed and its performance was affected by the cost of sampling and the resulting assessment of the environment proved unreliable. On the other hand, when prey body mass, but not abundance, varied among the patches the predator was quickly able to assess local profitability. Both body mass and survival of the predator were greatly affected by learning processes and patterns of food resource distribution.     

Fate and removal of typical pharmaceutical and personal care products in a wastewater treatment plant from Beijing: a mass balance study

The fate and removal of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs) has received great attention during the last decade. Numerous data concerning concentrations in the water phase can be found in the literature, however corresponding data from sludge as well as associated mass balance calculations are very limited. In the present study, the adsorbed and dissolved concentrations of 9 PPCPs were investigated in each unit of a WWTP in Beijing, China. Based on the calculation of mass balance, the relative mass distribution and removal efficiency of each target compound was obtained at each process. The amount of PPCPs entering into the WWTP ranged from 12 g·d^–1 to 3848 g·d^–1. Five target compounds (caffeine, chloramphenicol, bezafibrate, clofibric acid, and N,N-diethyl-meta-toluamide) were effectively removed, with rates of 57%–100%. Negative removal efficiencies were obtained for sulpiride, metoprolol, nalidixic acid, and carbamazepine, ranging from -19% to -79%. PPCPs mainly existed in dissolved form (≥92%) in both the raw influent and the final effluent. The sludge cake carried a much lower amount of PPCPs (17 g·d^–1) compared with the discharged effluent (402 g·d^–1). In A²/O treatment tanks, the anaerobic and anoxic tanks showed good performance for PPCPs removal, and the amount of adsorbed PPCPs was increased. The results reveal that both the dissolved and the adsorbed phases should be considered when assessing the removal capacity of each A²/O tank.     

袋式除尘器喷吹管设计参数对喷吹气量影响的计算分析

针对袋式除尘器的脉冲喷吹气流量不均匀性问题,利用CFD数值模拟建立含有结构参数、运行参数的脉冲袋式除尘器的喷吹气流分布模型,通过正交试验法研究了喷吹压力P、喷口个数N、喷口口径D、喷嘴管长H、脉冲时间T和喷口间距L对脉冲喷吹气流量不均匀性σ的影响程度,并拟合得到了各参数与σ的关系式。在设计压力条件下修正喷口管径,获得较好的气流量分布;对修正后的均匀喷吹管,得到在不同喷吹压力下其气流量不均匀性的变化情况。     

PM2.5中水溶性有机物吸光特性的模拟研究

研究建立了超声雾化器与光声光谱仪,扫描电迁移率颗粒物粒径谱仪联用的分析系统,将深圳市2011年夏季采集的PM2.5膜样品提取液雾化发生气溶胶,使之进入光声光谱仪检测其吸光强度以研究气溶胶中水溶性有机物(WSOM)的吸光特征.结果表明:观测期间PM2.5中WSOM平均质量浓度为(4.3±2.3)μg/m3,分别占PM2.5和OM质量浓度的11.9%±4.8%和49.2%±18.5%.WSOM在405,532,781nm波长下的质量吸收效率值(MAE)分别为(0.55±0.31),(0.54±0.31),(0.21±0.13)m2/g.经计算所得:深圳市夏季大气PM2.5中WSOM在405,532,781nm波长下的平均吸收系数分别为(2.30±1.08),(2.25±1.26),(0.86±0.45)Mm-1,对应的WSOM对大气PM2.5整体吸光效应的贡献率分别为7.6%,10.6%和5.8%,说明WSOM对PM2.5整体吸光效应的贡献不容忽视,有机气溶胶在大气灰霾中的能见度损害作用值得进一步深入研究.     

SPE-RRLC-MS/MS法测定制药废水中青霉素G

建立了利用固相萃取-高分离度快速液相色谱-串联质谱(SPE-RRLC-MS/MS)测定制药废水中青霉素G残留的方法。水样以30%硫酸锌+20%亚铁氰化钾作为沉淀剂沉淀蛋白质后,上清液采用Oasis HLB固相萃取柱富集和净化,以0.01 mol/L乙酸铵溶液(加0.1%甲酸)+乙腈作为流动相进行等度洗脱,经Agilent Plus C18柱分离后,在串联质谱ESI(+)源下进行MRM检测。该方法的青霉素G检出限(S/N=3)为0.02μg/L,目标物在0.0020～1.0 mg/L范围内线性关系良好,线性相关系数为0.9997。在0.20,1.0,2.0μg/L添加水平平均回收率为74.6%～101.4%,相对标准偏差为4.49%～8.17%。该方法灵敏度高、重现性好、定性定量准确,可满足制药废水中青霉素G残留检测的要求。     

Photodegradation of the herbicide goal

Photodegradation products of the herbicide Goal active ingredient were obtained with a xenon lamp and analyzed using direct inlet mass spectrometry, MS/MS and GC/MS. A number of products were identified and their generation pathways were established to be mainly Ar—O bond cleavage, dechlorination and photocyclisation. The latter process gives chlorinated and unchlorinated dibenzofurans some of which may be toxic.     

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.