Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min^?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m^?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

基于开源GIS的长江流域晴日辐射反演

以开源GIS软件GRASS为平台，首次通过辐射过程模型r.sun和编程语言Shell实现长江流域500 m分辨率的晴日辐射反演（包括直接辐射、散射辐射和反射辐射），为了解长江流域辐射时空分布规律和相关宏观气候、生态建模奠定基础。结论如下：（1）精度验证表明，晴日辐射反演结果较理想；相关晴日指数的误差指标MPE、MAPE和RMSE分别为37%、75%和64%，r.sun模型可进一步用于中国其它区域；（2）长江流域晴日辐射年均日值为2424±245 MJ/(m2·d)，其各组分差异显著，直接、散射、反射辐射分别占总辐射的842%、156%和02%；（3）晴日辐射空间分布梯度明显，沿三级地形阶梯向东辐射值及变异逐渐减小，海拔变化引起的大气衰减因素在决定晴日辐射分布时起重要作用；（4）晴日辐射季节分布不对称，月际变化总体呈倒“U”形分布；直接辐射和散射辐射变化趋势基本一致，但二者比例随大气浑浊度的变化波动剧烈。     

Perfluorinated compounds in whole fish homogenates from the Ohio, Missouri, and Upper Mississippi Rivers, USA

A method for the analysis of 10 perfluorinated compounds (PFCs) in whole fish homogenate is presented and applied to 60 fish samples collected from the Ohio, Missouri, and upper Mississippi Rivers in 2005. Method accuracy ranged between 86 and 125% with limits of quantitation between 0.2 and 10 ng/g wet weight. Intra- and inter-batch precision was generally ±20%. Perfluorooctane sulfonate (PFOS) was the predominant compound identified in these samples, contributing over 80% of total PFC composition in the fish from these rivers, with median PFOS concentrations of 24.4, 31.8, and 53.9 ng/g wet wt in the Missouri, Ohio, and Mississippi Rivers, respectively. Median PFOS levels were significantly (p = 0.01) elevated in piscivorous fish (88.0 ng/g) when compared with non-piscivorous fish (15.9 ng/g). The 10 samples with PFOS concentrations above 200 ng/g were broadly scattered across all three rivers, providing evidence of the widespread presence of this compound in these US waterways.     

Analytical methods and validation for determining trace elements in red wines

The objective of this work is to quantify As, Hg, Cd, Ni and Pb in Portuguese red wines. First, the methods for the quantification of trace elements in red wines were validated. Several pre-treatments were compared, namely a pre-digestion process with HNO₃, a pre-oxidation step with H₂O₂, and a spiking step of wine samples with a known concentration of the trace elements analyzed. Except for As, it was determined that the quantification of the trace elements does not require a pre-digestion process with HNO₃. For all of the trace elements analyzed, a pre-oxidation step with H₂O₂ may enable an accurate quantification. The techniques chosen for the quantification of trace elements were hydride generation atomic absorption spectrometry (HGAAS) for As and Hg, electrothermal atomic absorption spectrometry (ETAAS) for Cd, and flame atomic absorption spectrometry (FAAS) for Ni and Pb. In the second stage of this work, 25 Portuguese red wines spanning all of the red wine-producing regions were analyzed for all of the five trace elements referred to above. Only Cd and Pb have shown concentrations above the limit values defined by the “Organization Internationale de la Vigne et du Vin.” The Target Hazard Quotient (THQ) equation was used to determine in which wine-producing regions that wine consumption can be a problem for public health in terms of the concentrations of the five trace elements analyzed. THQ values have indicated that for the universe of the 25 red wines analyzed no region produces wines that can pose problems for public health, when the Portuguese red wine standard consumption is considered.     

Agreement between predicted risk and prevalence of Down syndrome in first trimester nuchal translucency screening

The agreement between predicted risks of Down syndrome and observed prevalence was investigated in a population of 11 847 singleton pregnancies screened by first trimester nuchal translucency at a single institution. Twenty-seven cases of Down syndrome were observed; 20 were detected prenatally by nuchal translucency and maternal age screening, three by other means and four postnatally. The screened women were grouped according to their predicted risk of having an affected pregnancy, and this was compared with the observed prevalence. A significant correlation between predicted and observed prevalences was noted, thus demonstrating that risk estimates for Down syndrome based on first trimester nuchal translucency screening are accurate. Copyright © 2002 John Wiley & Sons, Ltd.     

浅谈军用飞机外挂系统机械环境适应性设计鉴定流程

为了建立外挂系统机械环境适应性设计及鉴定流程,通过梳理外挂系统在使用寿命周期中预期会遇到的机械环境约束条件,确定外挂系统设计需要研究完成的内容,包括技术要求制定、验证/分析方法、试验/评估结果评定等。详细阐述了机械环境适应性设计必要性,正向定量/定性设计方法以及机械环境鉴定试验流程需要考虑的内容。形成了外挂系统机械环境设计及鉴定流程。以某外挂系统机械环境适应性设计鉴定为例,验证了流程的有效性及经济性。     

基于Stacking集成学习模型的气态亚硝酸预测

建立了基于Stacking集成学习下气态亚硝酸（HONO）预测模型.利用非相干宽带腔增强吸收光谱（IBBCEAS）系统获得的北京城区HONO的浓度,结合HONO的来源,选取了O₃、CO、SO₂、NO、NO₂、NO_y、温度（T）、相对湿度（RH）、风速（WS）、j（HONO）、j（NO₂）、j（O¹D）作为特征数据,通过对HONO的平均日变化分析,将测量时间按小时转换为新特征.分别以极端梯度提升（XGBoost）、轻量化梯度促进机（LightGBM）以及随机森林（RF）算法构建基模型,采用5折交叉验证的方式划分训练集,将基模型输出的结果作为新特征集,并将新特征集作为第二层线性回归模型的输入,通过对这两层中的模型进行训练,最终得到Stacking集成学习HONO预测模型.通过对模型的特征重要度分析和计算夜间交通直接排放所占的贡献,表明CO是模型预测中重要的影响因子,说明机动车的直接排放是该区域冬季时期HONO的重要来源.利用测试集分别对单模型和融合后模型的预测性能进行评估,3个单模型的预测结果与测量值的相关系数都达到了0.91以上,其中Stacking融合后的模型性能最好,相关系数达到了0.94,平均绝对误差和均方根误差分别为0.307×10^-9和0.453×10^-9,结果表明基于Stacking集成学习方式下HONO预测模型的可解释性和推广性.     

中国未来极端降水事件的变化——基于气候变化预估结果的分析

利用区域气候模式PRECIS单向嵌套Hadley气候中心海-气耦合模式HadCM3高分辨率的大气部分HadAM3P,分别进行了气候基准时段(1961—1990年)和2080 s时段(2071—2100年)中国区域各30年时间长度的模拟试验,以分析PRECIS对当代中国区域极端降水事件的模拟能力和SRES B2情景下2080s时段相对于气候基准时段中国区域极端降水事件的可能变化趋势。气候基准时段模拟结果与观测值的对比分析表明:PRECIS能够较好地模拟出中国区域年平均极端降水事件的空间分布特征,但模式模拟的大雨事件和湿日数高值区范围较观测值偏大,对华南地区暴雨事件和日最大降水事件的模拟结果较观测值偏低。SRES B2情景下,2080s时段年平均大雨事件除东北和华南地区外,全国均呈增多趋势。暴雨事件在西部地区以减少为主,而东部地区主要呈增加趋势。年平均日最大降水事件的分布型与大雨事件基本一致。湿日数除华北、西北和青藏高原部分地区外均呈减少趋势。未来长江流域洪涝灾害事件发生的频率将可能增大。     

快速路交通流异常数据判断算法研究及实证

对快速路交通流数据进行异常数据判断,有利于避免使用异常数据带来的损失,提高信息利用的有效性。笔者分别根据逻辑推理、交通流的重复性和连续性以及交通流变量之间的机理分析提出了3种判断快速路交通流异常数据的算法,并讨论了这3种算法之间的集成。利用北京快速路实测数据对算法进行了验证,验证结果表明该算法基本是有效的。     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 ± 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.