SELECTING TREND TESTS FOR WATER QUALITY SERIES WITH SERIAL CORRELATION AND MISSING VALUES1

ABSTRACT: The use of nonparametric tests for monotonic trend has flourished in recent years to support routine water quality data analyses. The validity of an assumption of independent, identically distributed error terms is an important concern in selecting the appropriate nonparametric test, as is the presence of missing values. Decision rules are needed for choosing between alternative tests and for deciding whether and how to pre-process data before trend testing. Several data pre-processing procedures in conjunction with the Mann-Kendall tau and the Seasonal Kendall test (with and without serial correlation correction) are evaluated using synthetic time series with generated serial correlation and missing data. A composite test (pre-testing for serial correlation followed by one of two trend tests) is evaluated and was found to perform satisfactorily.     

Analysis of the Trend and Seasonal Cycle of Carbon Monoxide Concentrations in an Urban Area (4 pp)

Background, Aim and Scope Air quality is an field of major concern in large cities. This problem has led administrations to introduce plans and regulations to reduce pollutant emissions. The analysis of variations in the concentration of pollutants is useful when evaluating the effectiveness of these plans. However, such an analysis cannot be undertaken using standard statistical techniques, due to the fact that concentrations of atmospheric pollutants often exhibit a lack of normality and are autocorrelated. On the other hand, if long-term trends of any pollutant’s emissions are to be detected, meteorological effects must be removed from the time series analysed, due to their strong masking effects. Materials and Methods The application of statistical methods to analyse temporal variations is illustrated using monthly carbon monoxide (CO) concentrations observed at an urban site. The sampling site is located at a street intersection in central Valencia (Spain) with a high traffic density. Valencia is the third largest city in Spain. It is a typical Mediterranean city in terms of its urban structure and climatology. The sampling site started operation in January 1994 and monitored CO ground level concentrations until February 2002. Its geographic coordinates are W0°22′52″ N39°28′05″ and its altitude is 11 m. Two nonparametric trend tests are applied. One of these is robust against serial correlation with regards to the false rejection rate, when observations have a strong persistence or when the sample size per month is small. A nonparametric analysis of the homogeneity of trends between seasons is also discussed. A multiple linear regression model is used with the transformed data, including the effect of meteorological variables. The method of generalized least squares is applied to estimate the model parameters to take into account the serial dependence of the residuals of this model. This study also assesses temporal changes using the Kolmogorov-Zurbenko (KZ) filter. The KZ filter has been shown to be an effective way to remove the influence of meteorological conditions on O₃ and PM to examine underlying trends. Results The nonparametric tests indicate a decreasing, significant trend in the sampled site. The application of the linear model yields a significant decrease every twelve months of 15.8% for the average monthly CO concentration. The 95% confidence interval for the trend ranges from 13.9% to 17.7%. The seasonal cycle also provides significant results. There are no differences in trends throughout the months. The percentage of CO variance explained by the linear model is 90.3%. The KZ filter separates out long, short-term and seasonal variations in the CO series. The estimated, significant, long-term trend every year results in 10.3% with this method. The 95% confidence interval ranges from 8.8% to 11.9%. This approach explains 89.9% of the CO temporal variations. Discussion The differences between the linear model and KZ filter trend estimations are due to the fact that the KZ filter performs the analysis on the smoothed data rather than the original data. In the KZ filter trend estimation, the effect of meteorological conditions has been removed. The CO short-term componentis attributable to weather and short-term fluctuations in emissions. There is a significant seasonal cycle. This component is a result of changes in the traffic, the yearly meteorological cycle and the interactions between these two factors. There are peaks during the autumn and winter months, which have more traffic density in the sampled site. There is a minimum during the month of August, reflecting the very low level of vehicle emissions which is a direct consequence of the holiday period. Conclusions The significant, decreasing trend implies to a certain extent that the urban environment in the area is improving. This trend results from changes in overall emissions, pollutant transport, climate, policy and economics. It is also due to the effect of introducing reformulated gasoline. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of CO. The KZ filter has been the most effective method to separate the CO series components and to obtain an estimate of the long-term trend due to changes in emissions, removing the effect of meteorological conditions. Recommendations and Perspectives Air quality managers and policy-makers must understand the link between climate and pollutants to select optimal pollutant reduction strategies and avoid exceeding emission directives. This paper analyses eight years of ambient CO data at a site with a high traffic density, and provides results that are useful for decision-making. The assessment of long-term changes in air pollutants to evaluate reduction strategies has to be done while taking into account meteorological variability     

金属表面涂装行业VOCs排放特征及排放系数

对比了浙江省2014和2018年金属表面涂装企业的有机废气排放及治理情况,分析了该行业涂料及稀释剂的使用、主要污染因子,测算了溶剂型、水性涂料的挥发性有机物（VOCs）产生系数和排放系数.结果表明：2018年VOCs治理水平明显高于2014年,水性涂料使用企业比例由18%上升至36%,纯溶剂型企业由82%下降至64%;金属表面涂装行业的主要排放污染物为二甲苯、丁醇、乙酸乙酯、乙酸丁酯、甲苯、丙二醇、乙苯、苯乙烯等8种有机物.溶剂型和水性涂料的VOCs产生系数分别为0.72和0.31kg/kg;溶剂型和水性涂料2014年VOCs排放系数为0.64和0.29kg/kg,2018年为0.48和0.21kg/kg.     

特殊区域地表水环境背景值表征技术方法研究与应用

选取黑龙江省源头水保护区作为研究对象,根据DEM数据对保护区内随机布设的水质监测点控制单元进行划分并提取单元内的相关指标建立监测点背景特性量化模型,基于量化结果提出地表水环境背景值监测方案,建立背景值数据库.选取研究区自然属性指标与空间属性指标,以空间叠置技术与聚类分析方法对研究区地表水进行背景值分区,最终将黑龙江省分为六大地表水水质背景值地理分区,并计算了各分区地表水环境背景值表征范围.表征范围显示：依据现行标准进行水质评价,保护区内水质背景值已超出Ⅱ类水质标准限值.因此,基于水质背景值研究成果提出了考虑背景值影响下的水环境质量评价方法,并将方法应用于研究区,结果表明方法切实可行且优于单因子评价法.研究成果可为区域制定背景值影响下的水环境评价方法提供科学的数据支撑与理论依据.     

纤维增强气凝胶复合材料高温结构转变及热稳定性研究

目的研究高温受热条件下纳米复合隔热材料的结构转变特征及热稳定性。方法采用扫描电镜、X射线衍射仪、红外光谱仪及热重仪等检测方法。结果纤维增强气凝胶材料从室温到650℃存在连续的质量损失,从室温到放热前,质量损失为1.66%;365℃开始出现放热,温度升至398℃时达到峰值,整个放热过程对应质量损失约为1.3%;从435℃放热结束开始到650℃的质量损失为1.46%。经过400℃热处理后,试样比表面积从268m~2/g增加到437m~2/g;当试样热处理温度达到600℃时,试样的比表面积明显随之降低至198m~2/g。结论 SiO_2气凝胶复合材料以无定形结构为主,存在少量的二氧化钛晶体。在400℃左右,SiO_2气凝胶结构中硅甲基Si—CH_3发生氧化,产生明显的放热峰,之后硅羟基Si—OH之间发生缩聚反应,使600℃热处理后气凝胶中Si—O—Si网络骨架强度有所提高。未处理的纤维增强气凝胶材料试样上气凝胶纳米颗粒构成的块体较为良好地包裹在玻璃纤维表面,而经过600℃的高温热处理1 h后,块体气凝胶脱离了光滑的纤维表面,气凝胶纳米粒子发生收缩,致使材料比表面积下降。     

海州湾表层沉积物磷的吸附容量及潜在释放风险

利用磷吸附指数（PSI）、磷吸附饱和度（DPS）和磷释放风险指数（ERI）研究了2016年10月和2017年5月海州湾表层沉积物的磷吸附容量及潜在释放风险.结果显示,2016年秋季PSI变化范围为99.58~199.39[mgP/（100g）]/[μmol/L],DPS变化范围为23.118%~34.289%;2017年夏季PSI变化范围是130.29~198.57[mgP/（100g）]/[μmol/L],DPS变化范围为25.545%~42.135%,两次调查中PSI和DPS均表现出相反的平面分布趋势.PSI和Al_ox、Fe_ox呈显著正相关,说明Fe_ox和Al_ox是影响海州湾表层沉积物吸附磷的主要因素,且Fe_ox占主导作用;DPS与Al_ox和Fe_ox分别表现出了显著负相关性和极显著负相关性,说明Al_ox和Fe_ox含量的增大会降低表层沉积物的磷吸附饱和度.2016年10月磷释放风险指数（ERI）的变化范围为11.59%~34.18%,2017年5月磷释放风险指数（ERI）的变化范围为12.86%~32.34%,从2次调查结果整体来看,海州湾表层沉积物的磷释放风险为中度风险.     

石墨烯在防腐涂料中的研究进展及应用

简要叙述了石墨烯结构性能以及当前主流制备石墨烯的方法。概述了最近几年来石墨烯在防腐涂料中的研究进展情况,包括石墨烯在涂料中的添加量、分散技术、原位改性等对涂料性能的影响。研究表明,在涂层中分散均匀添加量适中的石墨烯可以对防腐涂料性能有较大的提升,探讨了石墨烯在防腐涂层中的应用机理,同时对石墨烯防腐涂料的应用发展进行了展望。     

西安市文教区表层土壤中PAHs来源及风险分析

文教区土壤环境质量直接影响学生以及职工的身体健康。本研究应用高效液相色谱仪对采集的西安市文教区表层土壤样品中的16种优控多环芳烃(PAHs)进行含量检测,分析其组分特征、来源及健康风险。结果表明,西安市文教区表层土壤中∑PAHs含量为0.290~4.147μg/g,平均值为1.515μg/g,7种致癌多环芳烃的含量为0.079~2.093μg/g,均值为0.593μg/g,土壤PAHs污染较为严重。其中4环的高环PAHs为土壤PAHs污染的主要物质,平均占∑PAHs含量的40.72%。源解析结果表明西安市文教区表层土壤中PAHs主要来源于石油燃烧、煤及生物质等的不完全燃烧。终生癌症风险评价表明西安市文教区表层土壤中PAHs污染对其生活在周围的人群产生的终生致癌风险性较小,但71.4%的样点达到严重污染水平,产生的间接影响应引起足够重视。     

Water Quality Evaluation and Trend Analysis in Selected Watersheds of the Atlantic Region of Canada

Water quality indices (WQIs) have been developed to assess the suitability of water for a variety of uses. These indices reflect the status of water quality in lakes, streams, rivers, and reservoirs. The concept of WQIs is based on a comparison of the concentration of contaminants with the respective environmental standards. The number, frequency, and magnitude by which the environmental standards for specific variables are not met in a given time period are reflected in WQIs. Further, the water quality trend analysis predicts the behavior of the water quality parameters and overall water quality in the time domain. In this paper, the concept of WQI was applied to three selected watersheds of Atlantic region: the Mersey River, the Point Wolfe River, and the Dunk River sites. To have robust study, two different water quality indices are used: Canadian Water Quality Index (CWQI), and British Columbia Water Quality Index (BWQI). The complete study was conducted in two steps. The first step was to organize and process the data into a format compatible with WQI analysis. After processing the input data, the WQI was calculated. The second step outlined in the paper discusses detailed trend analysis using linear and quadratic models for all the three sites. As per the 25 years trend analysis, overall water quality for agriculture use observed an improving trend at all the three sites studied. Water quality for raw water used for drinking (prior to treatment) and aquatic uses has shown improving trend at Point Wolfe River. It is further observed that pH, SO₄, and NO₃ concentrations are improving at Dunk River, Mersey River, and Point Wolfe River sites. To ascertain the reliability and significance of the trend analysis, a detailed error analysis and parametric significance tests were also conducted It was observed that for most of the sites and water uses quadratic trend models were a better fit than the linear models.     

Trace Metal Concentration in Roadside Surface Soil and Tree Back: A Measurement of Local Atmospheric Pollution in Abuja, Nigeria

Cadmium, copper, lead, nickel and zinc concentrations were analysed by atomic absorption spectrophotometry in surface soil and tree bark from different districts of Abuja, Nigeria, in order to determine the atmospheric trace metal input in the area.Elevated concentrations of some of the studied metals were observed in the soil and tree bark samples from the commercial/high traffic areas of the city compared to backgroundvalues. In soil samples, the average concentration of the metals were 0.6±0.4, 18.0±4.0, 281±39, 16±4 and66±23 g g^-1 dry weight for Cd, Cu, Pb, Ni and Zn, respectively, whilst the average concentrations in tree bark were 0.3±0.2, 12±4, 133±32, 13±3 and 61±10 g g^-1 dry weight for Cd, Cu, Pb, Ni and Zn, respectively. The trend in trace metal levels suggested that automobile emissions are a major source of these metals as the highest concentrations of Pb and Zn were recorded in the commercial areas of the city known for their high traffic densities. The levels of metal in the study area were relativelylow compared to levels found in some larger and older cities in various countries worldwide.