USING UNCENSORED TRACE-LEVEL MEASUREMENTS TO DETECT TRENDS IN GROUND WATER CONTAMINATION1

ABSTRACT: Environmental decision making involving trace-levels of contaminants can be complicated by censoring, the practice of reporting concentrations either as less than the limit of detection (LOD) or as not detected (ND) when a test result is less than the LOD. Censoring can result in data series that are difficult to meaningfully summarize, graph, and analyze through traditional statistical methods. In spite of the relatively large measurement errors associated with test results below the LOD, simple and meaningful analyses can be carried out that provide valuable information not available if data are censored. For example, an indication of increasing levels of contamination at the fringe of a plume can act as an early warning signal to trigger further study, an increased sampling frequency, or a higher level of remediation at the source. This paper involves the application of nonparametric trend analyses to uncensored trace-level groundwater monitoring data collected between March 1991 and August 1994 on dissolved arsenic and chromium for seven wells at an industrial site in New York.     

ESTIMATING CENTRAL TENDENCY FROM UNCENSORED TRACE LEVEL MEASUREMENTS1

ABSTRACT: The statistical analysis of data which have trace level measurements has traditionally been a two-step process in which data are first censored using criteria based on measurement precision, and then analyzed with statistical methods for censored data. The process might be more informative if data were left uncensored. In this paper, information loss attributable to censoring and measurement noise are assessed by comparing the sample mean and median of uncensored measurements with a log regression mean and median based on censored data. Measurements are derived from lognormal parent distributions which have random variability characteristic of trace level measurement. The relative performance of estimators used with error-free samples and with samples having measurement noise can be explained by differences between the probability distributions of parents and measurements. Measurement introduces bias and dispersion and transforms lognormal parent distributions toward greater symmetry. Estimates using uncensored data are less biased and more accurate than the log regression mean and median when censoring exceeds about 50 percent, and are not much worse at any fraction censored. For data with many (80 percent) results below the limit of detection, bias may be quite severe.     

ESTIMATING MEAN AND VARIANCE FOR ENVIRONMENTAL SAMPLES WITH BELOW DETECTION LIMIT OBSERVATIONS1

ABSTRACT: Left-censoring of data sets complicates subsequent statistical analyses. Generally, substitution or deletion methods provide poor estimates of the mean and variance of censored samples. These substitution and deletion methods include the use of values above the detection limit (DL) only, or substitution of 0, DL/2 or the DL for the below DL values during the calculation of mean and variance. A variety of statistical methods provides better estimators for different types of distributions and censoring. Maximum likelihood and order statistics methods compare favorably to the substitution or deletion methods. Selected statistical methods applicable to left-censoring of environmental data sets are reviewed with the purpose of demonstrating the use of these statistical methods for coping with Type I (and Type II) left-censoring of normally and log-normally distributed environmental data sets. A PC program (UNCENSOR) is presented that implements these statistical methods. Problems associated with data sets with multiple DLs are discussed relative to censoring methods for life and fatigue tests as recently applied to water quality data sets.     

PESTICIDES IN GROUND WATER: DO ATRAZINE METABOLITES MATTER?1

ABSTRACT: Atrazine and atrazine-residue (atrazine + two metabolites - deethylatrazine and deisopropylatrazine) concentrations were examined to determine if consideration of these atrazine metabolites substantially adds to our understanding of the distribution of this pesticide in groundwater of the midcontinental United States. The mean of atrazine.residue concentrations was 53 percent greater than that of atrazine alone for those observations above the detection limit (> 0.05 μg/l). Furthermore, a censored regression analysis using atrazine-residue concentrations revealed significant factors not identified when only atrazine concentrations were used. Thus, knowledge of concentrations of these atrazine metabolites is required to obtain a true estimation of risk of using these aquifers as sources for drinking water, and such knowledge also provides information that ultimately may be important for future management policies designed to reduce atrazine concentrations in ground water.     

ESTIMATING THE MEAN AND VARIANCE OF CENSORED PHOSPHORUS CONCENTRATIONS IN FLORIDA RAINFALL1

ABSTRACT: The total phosphorous (TP) concentrations in the South Florida rainfall have been recorded in weekly intervals with a detection limit (D_L) of 3.5 μg/L. As a large amount of the data is reported as below the D_L, appropriate statistical methods are needed for data analysis. Thus, an attempt was made to identify an appropriate method to estimate the mean and variance of the data. In particular, a method to separate the statistics for the below D_L portion from the estimated population statistics is proposed. The estimated statistics of the censored data are compared with the statistics of the uncensored data available from the recent years’ laboratory records. It was found that the one-step restricted maximum likelihood method is the most accurate for the wet TP data, and that the proposed method to combine the estimated statistics for TP < D_L portion and the sample statistics for TP ≥ D_L portion improves estimates compared to the conventional maximum likelihood estimates.     

A simple high performance liquid chromatography method for analyzing paraquat in soil solution samples

A high performance liquid chromatography (HPLC) method with UV detection was developed to analyze paraquat (1,1'-dimethyl-4,4'-dipyridinium dichloride) herbicide content in soil solution samples. The analytical method was compared with the liquid scintillation counting (LSC) method using 14C-paraquat. Agreement obtained between the two methods was reasonable. However, the detection limit for paraquat analysis was 0.5 mg L(-1) by the HPLC method and 0.05 mg L(-1) by the LSC method. The LSC method was, therefore, 10 times more precise than the HPLC method for solution concentrations less than 1 mg L(-1). In spite of the high detection limit, the UC (nonradioactive) HPLC method provides an inexpensive and environmentally safe means for determining paraquat concentration in soil solution compared with the 14C-LSC method.     

A TECHNIQUE FOR ESTIMATING MONTHLY GLOBAL RADIATION1

ABSTRACT: A technique is presented for estimating monthly sums of global radiation from a combination of calculations of monthly cloudless global radiation, surface meteorological observations, and empirical equations relating sunshine to global radiation. The percent deviation of calculated from observed values is not negligible but is much less than errors obtained using extraterrestrial solar radiation sums. If monthly global radiation is estimated for areas other than the one area described here, the possible errors should be redetermined. Techniques to adapt the equations for other areas are discussed.     

TESTING FOR TREND IN LAKE AND GROUND WATER QUALITY TIME SERIES1

ABSTRACT: The detection of gradual trends in water quality time series is increasing in importance as concern grows for diffuse sources of pollution such as acid precipitation and agricultural non-point sources. A significant body of literature has arisen dealing with trend detection in water quality variables that exhibit seasonal patterns. Much of the literature has dealt with seasonality of the first moment. However, little has been mentioned about seasonality in the variance, and its effect upon the performance of trend detection techniques. In this paper, eight methods of trend detection that arise from both the statistical literature as well as the water quality literature have been compared by means of a simulation study. Varying degrees of seasonality in both the variances and the means have been introduced into the artificial data, and the performances of these procedures are analyzed. Since the focus is on lake and ground water quality monitoring, quarterly sampling and short to moderate record lengths are examined.     

ICP—OES法在测定降水中金属离子的研究

本文主要研究了应用电感耦合等离子体发射光谱法（ICP—OES法）同时测定降水中钾、钠、钙、镁金属离子的应用。通过多次测试待测标准物质,确定各待测元素的最佳分析谱线和仪器的工作参数。根据ICP-OES法测定模拟降水混合标准样品、降水样品及其加标样品的结果,与AAS法（原子吸收分光光度法）进行实验室间比对测定,得出ICP—OES法测定降水中钾、钠、钙、镁各离子的检出限、线性范围、标准偏差、准确度等均比AAS法得到的结果要好。ICP-OES法与国家标准方法——原子吸收分光光度法（GB13580．12—92,GB13580．13—92）相比,具有操作简单、多种元素同时测定、方便快捷、检出限低、线性范围宽、干扰少等优点;有良好的准确度和精密度,相对标准偏差在0．3％～1．5％之间,加标回收率在97％～105％之间;该方法明显优于国家标准方法。     

利用毛细管柱测定水和废水中的苯系物

本文研究了利用毛细管柱分离、测定水样中的苯系物。该方法用二硫化碳萃取水样中的苯系物,细口径毛细管柱分离,ＦＩＤ测定。在分流比为１００∶１的条件下,方法最低检出浓度在００２５～００４７ｍｇ／Ｌ之间,低于填充柱法。该方法适用于地表水、地下水和废水中微量苯系物的测定。     

NONPARAMETRIC APPROACHES TO ENVIRONMENTAL IMPACT ASSESSMENT1

ABSTRACT: The interesting developments in non-parainetric testing and estimation methods presented in the upcoming sequence of nine papers are evaluated, compared, and put into proper perspective. Because a deterioration in water quality constitutes a direct threat to human health, it is of utmost importance to have flexible non-parametric methods available for detecting and describing trends in water quality time series. A distinct advantage of nonparametric tests is that they are usually very effective when applied to “messy” environmental data which may, for example, contain many missing observations and not be normally distributed. By applying their enhanced approaches for nonparametric methods to water quality time series, as well as employing well designed simulation experiments, the authors of the papers clearly demonstrate the efficacy of utilizing nonparametric tests in environmental impact assessment.     

REGIONAL DETECTION OF CHANGE IN WATER QUALITY VARIABLES1

ABSTRACT: The detection of change in a hydrologic varaible, particularly water quality, is a current problem. A method is presented for testing whether there has been a shift in the mean of a hydrologic variable based on the well established bivariate normal distribution theory. In this technique, the dependent, or target, and the independent, or control, variables are formed as weighted linear combinations of the mean values at a number of locations in a selected target and control area. The weighting factors are determined based on a mathematical programming technique which minimizes the conditional coefficient of variation thereby minimizing the number of observations required to detect a change of a preselected magnitude in the mean of the target area. The result is a situation where a savings in the number of observations required to detect a change is a consequence of adding more stations: the space-time tradeoff. Two applications of the technique are presented, the first using electrical conductivity (EC) data from two sets of river basins and the second using EC data from a set of basins as the target variable and annual discharge as the control. The results indicate that a significant savings in time can be achieved by using this method.     

ISOLATION AND DETECTION OF GIARDIA CYSTS FROM WATER USING DIRECT IMMUNOFLUORESCENCE1

ABSTRACT: A water-sampling apparatus used for the isolation and detection of Giardia cysts in water has been designed and tested. The sampling apparatus uses one of a variety of pumps or waterline pressure to move water through a filter. Two of the optional pumps are lightweight enough to make the apparatus portable and thus suitable for sampling in remote areas. This technique of sample processing produces good cyst recovery in much less time than is required with previously established methods. Giardia cysts are identified using direct immunofluorescence.     

水中隐孢子虫的检测技术

本文着重评述了水中隐孢子虫卵囊的检测技术,具体介绍了EPA1622法和1623法、流式细胞计、荧光原位杂交、SPR生物传感器以及PCR等方法,并对其操作技术、检测周期、回收率、检测限、可靠性、敏感性、稳定性以及能否种类鉴别等方面进行了比较。笔者认为我国应致力于开展快速检测卵囊活性与传染性的研究;随着IMS、细胞分类法等纯化手段不断完善,PCR技术对研究水中隐孢子虫的检测将会有更广阔的发展空间。     

UNCERTAINTIES IN ESTIMATING THE WATER BALANCE OF LAKES1

ABSTRACT: Evaluation of hydrologic methodology used in a number of water balance studies of lakes in the United States shows that most of these studies calculate one or more terms of the budget as the residual. A literature review was made of studies in which the primary purpose was error analysis of hydrologic measurement and interpretation. Estimates of precipitation can have a wide range of error, depending on the gage placement, gage spacing, and areal averaging technique. Errors in measurement of individual storms can be as high as 75 percent. Errors in short term averages are commonly in the 15-30 percent range, but decrease to about 5 percent or less for annual estimates. Errors in estimates of evaporation can also vary widely depending on instrumentation and methodology. The energy budget is the most accurate method of calculating evaporation; errors are in the 10–15 percent range. If pans are used that are located a distance from the lake of interest, errors can be considerable. Annual pan-to-lake coefficients should not be used for monthly estimates of evaporation because they differ from the commonly used coefficient of 0.7 by more than 100 percent. Errors in estimates of stream discharge are often considered to be within 5 percent. If the measuring section, type of flow profile, and other considerations, such as stage discharge relationship, are less than ideal errors in estimates of stream discharge can be considerably greater than 5 percent. Errors in estimating overland (nonchannelized) flow have not been evaluated, and in most lake studies this component is not mentioned. Comparison of several lake water balances in which the risdual consists solely of errors in measurement, shows that such a residual, if interpreted as ground water, can differ from an independent estimate of ground water by more than 100 percent.     

RAINGAGE NETWORK DESIGN USING NEXRAD PRECIPITATION ESTIMATES1

ABSTRACT: A general framework is proposed for using precipitation estimates from NEXRAD weather radars in raingage network design. NEXRAD precipitation products are used to represent space time rainfall fields, which can be sampled by hypothetical raingage networks. A stochastic model is used to simulate gage observations based on the areal average precipitation for radar grid cells. The stochastic model accounts for subgrid variability of precipitation within the cell and gage measurement errors. The approach is ideally suited to raingage network design in regions with strong climatic variations in rainfall where conventional methods are sometimes lacking. A case study example involving the estimation of areal average precipitation for catchments in the Catskill Mountains illustrates the approach. The case study shows how the simulation approach can be used to quantify the effects of gage density, basin size, spatial variation of precipitation, and gage measurement error, on network estimates of areal average precipitation. Although the quality of NEXRAD precipitation products imposes limitations on their use in network design, weather radars can provide valuable information for empirical assessment of rain‐gage network estimation errors. Still, the biggest challenge in quantifying estimation errors is understanding subgrid spatial variability. The results from the case study show that the spatial correlation of precipitation at subgrid scales (4 km and less) is difficult to quantify, especially for short sampling durations. Network estimation errors for hourly precipitation are extremely sensitive to the uncertainty in subgrid spatial variability, although for storm total accumulation, they are much less sensitive.     

DESIGN CONSIDERATIONS FOR AMBIENT STREAM QUALITY MONITORING1

ABSTRACT: Existing ambient water quality monitoring programs have resulted in data which are often unsuitable for assessment of water quality trends. A primary concern in designing a stream quality monitoring network is the selection of a temporal sampling strategy. It is extremely important that data for trend assessment be collected uniformly in time. Greatly superior trend detection power results for such a strategy as compared to stratified sampling strategies. In general, it is desirable that sampling frequencies be at least monthly but not greater than biweekly; higher sampling frequencies usually result in little additional information. An upper limit on trend detectability exists such that for both five and ten year base periods it is often impossible to detect trends in time series where the ratio of the trend magnitude to time series standard deviation is less than about 0.5. For the same record lengths trends in records with trend to standard deviation ratios greater than about one can usually be detected with very high power when a uniform sampling strategy is followed.     

THE EFFICIENCY OF WATER PRICING: A RATE OF RETURN ANALYSIS FOR MUNICIPAL WATER DEPARTMENTS1

ABSTRACT: The rate of return on invested capital can be used as a guide to resource allocation by municipal water departments (MWD's) in the same way it is used in the private sector. To achieve economic efficiency, the target rate of return for MWD's should be the market rate of return as an approximation to the opportunity cost of capital. The actual internal rate of return for a sample of 30 California MWD's for the period 1970-1982 is calculated for this study. The operating internal rate of return varies across the sample MWD's from less than 2 percent to 14 percent. If 10 percent is taken as the opportunity cost of capital, 25 of the 30 MWD's were inefficient; i.e., earned less than 10 percent. Half the sample earned less than 5 percent. An examination of potential causes of low rates of return shows that low average water prices are the primary reason for the low rates of return. For efficient operation, MWD's should set a target rate of return equal to the opportunity cost of capital and adjust water prices so as to achieve that target.     

Leaching of N-nitrosodimethylamine (NDMA) in turfgrass soils during wastewater irrigation

N-nitrosodimethylamine (NDMA) is a carcinogenic by-product of chlorination that is frequently found in municipal wastewater effluent. NDMA is miscible in water and negligibly adsorbed to soil, and therefore may pose a threat to ground water when treated wastewater is used for landscape irrigation. A field study was performed in the summer months under arid Southern California weather conditions to evaluate the leaching potential of NDMA in turfgrass soils during wastewater irrigation. Wastewater was used to irrigate multiple turfgrass plots at 110 to 160% evapotranspiration rate for about 4 mo, and leachate was continuously collected and analyzed for NDMA. The treated wastewater contained relatively high levels of NDMA (114-1820 ng L(-1); mean 930 ng L(-1)). NDMA was detected infrequently in the leachate regardless of the soil type or irrigation schedule. At a method detection limit of 2 ng L(-1), NDMA was only detected in 9 out of 400 leachate samples and when it was detected, the NDMA concentration was less than 5 ng L(-1). NDMA was relatively persistent in the turfgrass soils during laboratory incubation, indicating that mechanisms other than biotransformation, likely volatilization and/or plant uptake, contributed to the rapid dissipation. Under conditions typical of turfgrass irrigation with wastewater effluent it is unlikely that NDMA will contaminate ground water.