春季水华对南黄海总溶解态无机砷生物地球化学行为的影响

利用氢化物发生-原子荧光光谱法(HG-AFS)对2007年3月30日至4月23日南黄海海域总溶解态无机砷(TDIAs,[TDIAs]=[As5+]+[As3+])的含量进行了测定,其中针对水华中心区域(BM1站)进行了25h的连续观测,以探讨春季水华对有毒类金属元素砷的生物地球化学行为的影响。结果表明,TDIAs的浓度范围为7.9~22.3nmol/L,平均值为(17.8±1.9)nmol/L。TDIAs在南黄海的分布主要表现为由近岸向外海逐渐升高的趋势,最大值出现在南部海域底层海水中。近岸海域表、底层TDIAs的含量相当,而中、南部海域由于存在明显的密度跃层,表、底层TDIAs的浓度具有显著性差异。2007年3月31日至4月1日研究区域西南部受到沙尘天气和降雨的影响,表层海水中TDIAs的含量显著升高。研究区域中、南部海域在观测期间暴发了典型的黄海春季水华,通过大面观测和对重点区域的连续观测可以发现,水华期间TDIAs的分布和磷酸盐类似,与Chl a呈现出较好的负相关关系(r=0.51,P0.05,n=39)。经初步计算,浮游植物水华对10m以上表层水体中TDIAs的清除量约为2.4nmol/L,占表层保有量的15%左右。通过箱式模型计算得出黄海TDIAs的停留时间约为(18.2±8.5)a,远远低于大洋。通过对该海域砷、磷摩尔比值的计算可以发现,南黄海砷、磷摩尔比值约为大洋中的20倍左右,这可能会引起浮游生物对砷酸盐的大量吸收和转化,从而带来潜在的生态危机,需要引起足够的重视。     

弧形防波堤波浪力试验研究

在圆筒形防波堤和V形防波堤的基础上,结合离岸堤后形成V形和半圆形连续出现的韵律海岸的地貌平面形态特点,提出一种前墙为连续的半圆筒形防波堤形式。通过在波浪水槽内进行规则波物理模型试验,探究这一新型防波堤的波压力分布规律及波高、周期、水深等因素对波压力的影响。将试验结果与海港水文公式和合田良实公式计算的理论值对比分析,给出了以合田良实公式的折减系数来拟合新型弧形防波堤波浪总水平力的计算公式。结果表明:新型弧形防波堤上的波压力随波高、周期的增大而增大,其水平波浪总力比同等尺度直墙少10%左右。     

病态总体最小二乘问题的谱修正迭代法

针对病态问题岭估计法及正则化方法存在破坏方程的等量关系、解是有偏估计的问题,在最小二乘谱修正迭代法的基础上,提出病态总体最小二乘问题的谱修正迭代法,并推导了总体最小二乘谱修正迭代法及其改进算法的具体公式。通过算例验证和阐明了TLS谱修正迭代法在病态问题中的有效性和易受迭代初值影响的缺点。     

稳健估计下转换参数系数矩阵定向改正的整体最小二乘

不同空间坐标系在进行坐标转换过程中,利用整体最小二乘(TLS)构建高斯-马尔科夫(Gauss-Markov)模型求解布尔莎-沃尔夫(Bursa-Wolf)七参数模型时,存在已知控制点含有粗差、模型系数阵固定常数参与残差改正的问题。通过对系数矩阵中含误差参数进行改正,并结合稳健估计的方法,对TLS进行迭代定权,解决了已知控制点粗差会对参数计算精度产生影响的问题,同时使得系数矩阵中非常数项得到精确的残差改正。本文通过实验数据证明,此方法可行并且解算精度更优。     

Interannual and Decadal Variations of Surface Solar Radiation over East China in the First Half of the 20th Century

Variability and long-term trends of sunshine duration(SSD) and total cloud cover(TCC) were studied based on surface observations from 10 meteorological stations over East China in the first half of the 20 th century. The correlation coefficients between SSD and diurnal temperature range(DTR), as well as TCC, were analyzed. SSD experienced a significant increasing trend(0.16 h d-1 per decade) from 1908 to 1936, and the maximum brightening was in autumn(0.33 h d-1 per decade). The good agreement between the variability of SSD and DTR, supported by the correlation coefficient between them of 0.72, implies that the SSD measurements were reliable. TCC showed a decreasing trend(-0.93% per decade) and was significantly inversely related to SSD(-0.74), indicating the variation of SSD was attributable to changes in cloud cover. The result was obviously different to that since the 1960 s, when clouds could not account for the decadal trend of surface solar radiation in China.     

The total operating characteristic to measure diagnostic ability for multiple thresholds

The relative operating characteristic (ROC) is a popular statistical method to measure the association between observed and diagnosed presence of a characteristic. The diagnosis of presence or absence depends on whether the value of an index variable is above a threshold. ROC considers multiple possible thresholds. Each threshold generates a two-by-two contingency table, which contains four central entries: hits, misses, false alarms, and correct rejections. ROC reveals for each threshold only two ratios, hits/(hits + misses) and false alarms/(false alarms + correct rejections). This article introduces the total operating characteristic (TOC), which shows the total information in the contingency table for each threshold. TOC maintains desirable properties of ROC, while TOC reveals strictly more information than ROC in a manner that makes TOC more useful than ROC. We illustrate the concepts with an application to land change science.     

原子荧光测定食品中总砷方法的改进与探讨

针对国标《GB 5009.11—2003食品中总砷及无机砷的测定》中的原子荧光-湿法消解测定总砷的方法中存在的难于控制完全消解样品、测定结果不稳定,试剂用量大的问题,对原方法进行了3点改进。一是利用浓硫酸沸点高,能脱水碳化破坏有机物的特性,通过高温浓缩硫酸对样品进行两次脱水碳化消解,使样品消解的更完全,且节省试剂;二是针对样品中砷形态的多样性,加强温度控制,低温消解、降低易挥发砷化合物的损失,高温加速样品消解,缩短操作时间;三是加盖小漏斗制造回流,减少易挥发砷化合物的损失,使方法易操作、节省试剂。用改进的方法测定菠菜粉(GBW10015)、海带粉(GBW08517)和虾粉(CNAS T0442)中的总砷,不少于6个平行样的测定结果均位于参考值范围的中间部分,且RSD值均小于7%,表明改进的方法准确、稳定。结果还表明,200℃的硫酸、高氯酸的混合酸和高温浓硫酸均能有效消解样品中砷甜菜碱和砷糖类化合物。     

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