Inferences about the variability of means from censored data

In recent years, intensive biological monitoring studies have been carried out on the Niagara River by the Ontario Ministry of the Environment. The basic objective was to determine the relative bioavailability of trace contaminants at various locations in the river, and to identify sources. A recurring difficulty encountered with the generated data is that substantial portions of sample concentrations of many toxic pollutants are below the limits of detection established by analytical laboratories. Under the assumption that the distribution of the data is log normal, the likelihood ratio test for testing the equality of several means for type I censored data is derived and its use for evaluating the spatial variability of trace contaminants in the river is illustrated.     

Spatial modelling of the probability of obtaining a detectable concentration of ammonia in Moreton Bay, Australia

Ammonia is an important water quality variable, which in excess, can be detrimental to waterways and their ecosystems. In the Ecosystem Health Monitoring Program in South-east Queensland ammonia is monitored monthly, however, often more than 50% of the ammonia observations in Moreton Bay are below detection limit, making it difficult to draw useful inferences. In this paper a clipped Gaussian random field is used to spatially model and map the probability of detectable concentration of ammonia. The methodology is applied to the Moreton Bay samples collected in February 2005. The results suggest that for this month the oceanic impacted areas have higher probability of detectable ammonia concentration than the areas closer to the main sources of anthropogenic inputs.     

Bromate analysis in groundwater and wastewater samples

Bromate (BrO(3)(-)) is a disinfection by-product formed during ozonation of potable water supplies containing bromide (Br(-)). Bromate has been classed by the World Health Organisation as a 'possible human carcinogen', leading to implementation of 10-25 microg L(-1)(as BrO(3)(-)) drinking water limits in legislative areas including the United States and European Union. Techniques have been developed for bromate analysis at and below regulatory limits, with Ion Chromatography (IC) coupled with conductivity detection (IC-CD), post-column reaction and ultra-violet (UV) detection (IC-PCR), or inductively coupled plasma-mass spectrometry detection (IC-ICPMS) in widespread use. The recent discovery of bromate groundwater contamination in a UK aquifer has led to a requirement for analysis of bromate in a groundwater matrix, for environmental monitoring and development of remediation strategies. The possibility of bromate-contaminated water discharge into sewage treatment processes, whether accidental or as a pump-and-treat strategy, also required bromate analysis of wastewater sources. This paper summarises techniques currently available for trace bromate analysis in potable water systems and details studies to identify a methodology for routine analysis of groundwater and wastewater samples. Strategies compared were high performance liquid chromatography (HPLC) with direct UV or PCR/UV detection, IC-CD, IC-PCR, and a simple spectrophotometric technique. IC-CD was the most cost-effective solution for simultaneous analysis of bromate and bromide within groundwater samples, having a 5 microg L(-1) detection limit of both anions with limited interference from closely-eluting species. Wastewater samples were successfully analysed for bromate only using HPLC with PCR/UV detection, with detection limits below 20 microg L(-1)(as BrO(3)(-)) and low interference. HPLC with direct UV detection was unsuitable for bromate analysis within the concentration range 50-5000 microg L(-1) which was required for this project, but column choice was shown to be a major factor in determining limits of detection. Spectrophotometry could not reproducibly determine bromate concentration, although the technique showed promise as a quick field method for high-level groundwater bromate analysis.     

高效液相色谱法测定地表水中四乙基铅

系统研究了地表水中四乙基铅的液相色谱分析方法,水中四乙基铅经二氯甲烷萃取浓缩后,用高压液相色谱柱分离,在280 nm波长处检测,根据保留时间定性,外标法定量,检出限及测定下限分别为0.02μg/L和0.06μg/L,低于地表水限值0.1μg/L,地表水平行测定的相对标准偏差均小于5%,地表水和废水样品加标回收率分别为79.4%～82.0%和62.5%～106.6%。     

羊角铺水源水中极微量NO -2 - N的测定

建立了自制浮选器富集、分光光度法测定羊角铺水源水中痕量亚硝酸盐氮的方法,介绍了试验的注意事项。方法在0μg／L-4．00μg／L范围内线性良好,检出限为0．0002mg／L,RSD为2．0％-4．6％,加标回收率为94．0％-108％。     

饮用水源中挥发性有机物分析方法的优化和应用

采用吹扫捕集—气相色谱—质谱联用技术分析水中的24种挥发性有机物。通过优化分析条件,改善了各组份的分离效果,节省了分析时间,得到各组份检测限为0.001-0.099μg/L,相对标准偏差为2.3%-5.6%,加标回收率为91.2%-107.6%,方法具有较好的精密度、准确度和低检测限。同时对漳州市饮用水源中的24种挥发性有机物进行监测分析,结果均低于检测限。     

Lognormality of trace contaminant concentrations in sewage effluents

It is important to understand the statistical distribution of monitoring data for them to be of value in determining the parameters of environmental models. No such distributional information has been available for many trace contaminants in sewage effluents. This paper applies the data of a major UK sewage works’ effluent monitoring programme to determine the validity of the common assumption that data are lognormally distributed. Effluent quality was monitored at 162 wastewater treatment works over 1 year, generating over 3,000 results for each of over 40 substances, including metals, trace organic substances and pharmaceuticals. It is demonstrated that the lognormal assumption is clearly justified for the great majority of substances in the spatial case—for annual average effluent concentrations across different treatment works. In the site-specific, temporal case—for individual determinations of concentration at a single site over an annual period—lognormality is generally supported but not demonstrated so unequivocally for all site/substance combinations. The principal source of uncertainty was lack of sufficient numbers of observations reported to adequately low reporting limits.     

地表水超痕量苯并(a)芘的检测及空白干扰消除

采用液液萃取-超高效液相色谱仪接荧光检测器测定地表水中超痕量的苯并(a)芘,并对方法空白的干扰因素进行探讨。研究发现,该法的空白干扰主要来自于溶剂二氯甲烷,溶剂经蒸馏提纯后可消除干扰。以重新蒸馏提纯的二氯甲烷为提取剂,方法的检测限为0.05 ng/L,加标回收率为87.4%~132%,且空白测定值低于方法检出限,可满足地表水中超痕量苯并(a)芘检测的需求。     

无机痕量分析中预富集技术的应用现状及前景

综述了预富集技术在无机痕量分析中的应用，概述了国内外最新进展，介绍了主要技术及方法的特点，大量文献表明预富集技术用于痕量分析取得满意的效果，降低了检测限，提高了灵敏度。     

饮用水源中痕量联苯胺的检测方法

建立了固相萃取高效液相色谱水中联苯胺的检测方法。选择Waters HLB固相萃取小柱富集水样,二氯甲烷/丙酮洗脱,以甲醇-水(pH=8,0.02 mol/L磷酸盐缓冲体系)作为流动相,保留时间为3.850 min,检测波长285 nm,0.1～10.0 mg/L范围内线性关系好,相关系数为0.999,检出限达到8×10-6mg/L,相对标准偏差为4.0%～9.5%,不同浓度样品加标回收率为80.5%～102.5%。     

Climate dynamics and extreme precipitation and flood events in Central Europe

Past changes and possible future variations in the nature of extreme precipitation and flood events in Central Europe and the Alpine region are examined from a physical standpoint. An overview is given of the following key contributory physical processes: (1) the variability of the large-scale atmospheric flow and the associated changes of the North-Atlantic storm track; (2) the feedback process between climate warming and the water cycle, and in particular the potential for more frequent heavy precipitation events; and (3) the catchment-scale hydrological processes associated with variations in major river flooding events and that are related to land-use changes, river training measures, and shifts in the proportion of rain to snowfall. In this context an account is provided of the possible future forecasting and warning methodologies based upon high-resolution weather prediction and runoff models. Also consideration is given to the detectability of past (future) changes in observed (modeled) extreme events. It is shown that their rarity and natural fluctuation largely impedes a detection of systematic variations. These effects restrict trend analysis of such events to return periods of below a few months. An illustration using daily precipitation from the Swiss Alps does yield evidence for pronounced trends of intense precipitation events (return period 30 days), while trends of stronger event classes are not detectable (but nevertheless can not be excluded). The small detection probability for extreme events limits possible mitigation of future damage costs through an abatement of climate change alone, and points to the desirability of developing improved early forecasting/warning systems as an additional no-regret strategy. This revised version was published online in July 2006 with corrections to the Cover Date.     

A multi-variate methodology for analyzing pre-existing lake water quality data

Environmental agencies are given the task of monitoring water quality in rivers, lakes, and other bodies of water, for the purpose of comparing the results with regulatory standards. Monitoring follows requirements set by regulations, and data are collected in a systematic way for the intended purpose. Monitoring enables agencies to determine whether water bodies are polluted. Much effort is spent per monitoring event, resulting in hundreds of data points typically used solely for comparison with regulatory standards and then stored for little further use. This paper devises a data analysis methodology that can make use of the pre-existing datasets to extract more useful information on water quality trends, without new sample collection and analysis. In this paper, measured lake water quality data are subjected to statistical analyses including Principal Component Analysis (PCA) to deduce changes in water quality spatially and temporally over several years. It was found that the lake as a whole changed temporally by season, rather than spatially. Storm events caused the greatest shifts in water quality, though the shifts were fairly consistent across sampling stations. This methodology can be applied to similar datasets, especially with the recent emphasis by the U.S. EPA on protection of lakes as water sources. Water quality managers using these techniques may be able to lower their monitoring costs by eliminating redundant water quality parameters found in this analysis.     

Robust graphical methods for diagnosing trend in irregularly spaced water quality time series

Graphical methods can play an important role in the reliable assessment of trends in typically ill behaved river quality data series both as diagnostic tools and as visual corroborative evidence when assumptions required for formal statistical tests are not met. Robust, graphically-oriented trend diagnosis procedures are presented for data series characterized by nonnormal populations, uneven time spacing, nonmonotonic trend and other factors which can create serious problems for standard parametric time series methods. Cleveland's robust locally weighted regression (RLWR) developed for investigating nonlinearity in x-y scatterplots is adapted as a robust/resistant smoothing filter for the analysis of irregular time series comprising quantitative observations. Low powered RLWR trend lines reveal temporally local phenomena, e.g. abrupt jumps (often associated with point source impacts) and periodicities, while higher powered RLWR yields smooth lines characterizing medium and longer term trends. Simple variants of Tukey smoothing concepts are developed for series with censored observations. Applications to Ontario river quality series reveal that graphical evidence is frequently sufficient to obviate the need for formal trend testing. The methods are generally applicable to most time series.     

Comparative assessment of pesticide residues in grain, soil, and water from IPM and non-IPM trials of basmati rice

The integrated pest management (IPM) modules of pesticide schedule on Basmati rice were validated at field experiments conducted in Northern India for consecutive 3 years (2005–2008). The pesticide residues were found below the detectable limit (<0.01–0.001 mg/kg) in soil and irrigation water samples of Kaithal region. In Dehra Dun region of Uttrakhand, the residues of carbendazim in rice grains and soil were detected below <0.01 mg/kg level. In second year experiments (2006–2007), only four non-IPM soil samples indicated the presence of chlorpyrifos and endosulfan in the range of ND <0.001 to 0.07 mg/kg, out of 45 samples analyzed. Carbendazim applied as seed treatment at Dehradun and Kaithal field trials was found below detectable limit in both IPM and non-IPM rice grains (<0.01 mg/kg) and irrigation water (0.01 μl/ml). Chlorpyrifos was detected in five water samples from Kaithal and one from Pant Nagar in the range of 0.003–0.006 μl/L, α- and β-isomer of endosulfan in the range of 0.005–0.03, and 0.005–0.02 μl/ml, respectively, in one sample from Pant Nagar and two from Kaithal, out of a total of 22 samples. In the region of Uttrakhand and Uttar Pradesh during 2007–2008, four non-IPM samples of soil indicated trace levels of endosulfan, out of 16 samples analyzed. The residues were detected below detection limit for carbendazim (<0.01 mg/kg) in soil samples of Dehradun IPM fields and for endosulfan and carbendazim (0.001–0.01 μl/L) in water samples each from IPM and non-IPM fields of Uttar Pradesh. The results of 3-year trials of IPM module indicated basmati rice as safe and economical with pesticide residue-free rice grains.     

电感耦合等离子体质谱法测定水中痕量元素

应用电感耦合等离子体质谱法对水样(地表水、饮用水等)中铜、锌、硒、砷、镉、铬、铅、铁、锰等痕量元素进行分析测定。结果表明,方法检出限为0.01~0.78μg/L,平行测定的相对标准偏差为0.6%~7.9%,实际水样加标回收率为90.5%~103%。该方法快速、简便、线性范围大,具有良好的检出限和准确度。     

Optical fiber based methodology for assessment of thiocyanate in seawater

A new methodology for the assessment of thiocyanate (SCN(-)) is proposed based on optical fiber (OF) detection coupled to a liquid chromatography system (LC). The developed methodology showed an adequate performance for the analysis of SCN(-) comparable to a high performance liquid chromatography with UV detector (HPLC-UV) methodology: a detection limit of 3 μg L(-1), a linear range from 4 to 400 μg L(-1), and an analytical time of less than 6 min. The OF based methodology was of compact design and easy operation. This simple system has the potential to be used as a sensing approach for SCN(-) in seawater.     

液相色谱法测定土壤中苯并(a)芘

用快速溶剂萃取法ASE300对土壤样品进行前处理,以配有荧光检测器的高效液相色谱仪分析土壤样品中苯并(a)芘的含量,该方法以乙腈、水梯度比例混合作为流动相,流速为1.0 ml/min;激发波长和发射波长分别为255 nm和420 nm;保留时间为27.58 min。样品的称样量为25 g时,测定检出限为8.28×10-5mg/kg,相对标准偏差(RSD)为1.0%~12%,回收率为60%~87%,以上指标均能满足环境中土壤样品的检测要求。     

Intra- and intercompartmental associations between levels of organochlorines in maternal plasma, cord plasma and breast milk, and lead and cadmium in whole blood, for indigenous peoples of Chukotka, Russia

Long-range transport of pollutants towards circumpolar regions emphasizes the need for up-to-date and reliable biological monitoring data. This paper explores the use, reliability and availability of maternal blood (MB) and plasma (MP), cord blood (CB) and plasma (CP) and mother's milk (MM) in terms of assessing exposure to persistent toxic substances (PTSs). It is concluded that MP has the best combination of availability, sensitivity in terms of number of PTSs, their detection frequency and concentrations, and physiological relevance. The study group consisted of 48 pregnant women of indigenous origin from the Chuchki district in the eastern Russian arctic. Blood, CB and MM specimens were collected from all women and MP, CP and MM were analyzed for the Arctic Monitoring and Assessment Programme (AMAP) suite of organochlorines (OCs) and metals (Pb and Cd in MB and CB). Generally speaking, the levels of PTSs coincided with those indicated in several AMAP publications from Chukotka and other areas of northern Russia. The correlations of PTS concentrations between the three body fluid compartments exceeded the minimum statistical requirements of alpha = 0.05 and beta = 0.20 for most of the compounds, with r > 0.46 except for Cd (r = 0.05); lipid adjustments for the OCs did not affect the r-values to any significant extent. The majority of the inter-OC correlations within compartments also fulfilled the indicated statistical condition. Careful consideration is given to the replacement of concentrations below the detection limit, OC detection frequency, the criteria for log-transformation of the data, analytical uncertainty, and biological variability. Practical implications of the findings are explored.     

Dose equivalent commitments from fallout radionuclides in the open waters of the Great Lakes. 1973–1981

The levels of ¹⁴⁴Ce, ¹³⁷Cs, ¹²⁵Sb, and ⁹⁰Sr in the open waters of the Great Lakes were measured over the period 1973–81. The levels were found to be very low. ¹⁴⁴Ce was detected only up to 1975 after which it dropped below the detection limit. The data indicate that the concentrations of the remaining three radionuclides have decreased with time. ⁹⁰Sr and ¹³⁷Cs provide essentially all of the radiological dose from drinking Great Lakes water. The dose equivalant commitments have been calculated from these measurements and found to be well within the Great Lakes Water Quality Agreement's water quality objective for radioactivity.     

Analyzing censored environmental data using survival analysis: Single sample techniques

The occurrence of censored data due to less than detectable measurements is a common problem with environmental data. The methods of survival analysis, although designed primarily for right censored data and time measured variables, can be adapted to apply censored environmental data. These methods have several theoretical and practical advantages over many existing techniques for dealing with less than detectable measurements.Work performed under the auspices of the U.S. Department of Energy, DOE Contract No. DE-AC07-76ID01570.