a study of the temporal variability of atrazine in private well water. part i: study design, implementation, and database development

In 1988, the Iowa Department of Natural Resources, along withthe University of Iowa conducted the Statewide Rural WellWater Survey, commonly known as SWRL. A total of 686private rural drinking water wells was selected by use of aprobability sample and tested for pesticides and nitrates. Sixty-eight of these wells, the 10% repeat wells, were additionallysampled in October, 1990 and June, 1991. Starting inNovember, 1991, the University of Iowa, with sponsorshipfrom the United States Environmental Protection Agency,revisited these wells to begin a study of the temporalvariability of atrazine and nitrates in wells. Other wells, whichhad originally tested positive for atrazine in SWRL but werenot in the 10% repeat population, were added to the studypopulation. Temporal sampling for a year-long period beganin February of 1992 and concluded in January of 1993. Allwells were sampled monthly, one subset was sampled weekly,and a second subset was sampled for 14-day consecutiveperiods. Two unique aspects of this study were the use of animmunoassay technique to screen for triazines before gaschromatography/mass spectrometry (GC/MS) analysis andquantification of atrazine, and the use of well owners to samplethe wells. A total of 1771 samples from 83 wells are in thefinal data base for this study. This paper reviews the studydesign, the analytical methodologies, and development of thedata base. A companion paper (Pinsky et al., 1997) discussesthe analysis of the data from this survey.     

Spatial Extent of Sediment Toxicity in U.S. Estuaries and Marine Bays

Acute, laboratory toxicity tests were performed by the National Oceanic and Atmospheric Administration (NOAA) on 1543 surficial sediment samples collected during 1991 through 1997 throughout 25 estuaries and marine bays. Selected areas were sampled along the Atlantic, Gulf of Mexico, and Pacific coasts. The toxicity of each sample was determined with 10-day amphipod survival tests performed with solid-phase (bulk) sediments. Collectively, the 1543 samples tested through 1997 represented a total area of approximately 7300 km². Toxicity was observed with the amphipod survival tests in samples that represented approximately 6% of the combined area. Using similar tests conducted on samples collected in different, but overlapping, study areas, the U.S. Environmental Protection Agency (EPA) estimated that approximately 7% of the combined estuarine area sampled was toxic. Generally, toxicity was most severe in northeastern and southwestern estuaries and least prevalent in southeastern and northwestern areas. However, considerable portions of the Pacific coast have not been tested with the same methods. In tests of CYP1A enzyme induction (n=464), samples were toxic that represented about 5% of the combined study areas. Toxicity was much more widespread, however, when the results of two sub-lethal tests were analyzed. Significant results occurred in samples that represented approximately 25% and 39% of the study areas in tests of sea urchin fertilization (n=1309) and microbial bioluminescence (n=1215), respectively.     

Network design factors for assessing temporal variability in ground-water quality

Benchmark major ions and nutrients data were collected biweekly for about two years at 12 wells at two sites in a shallow sand and gravel aquifer in west-central Illinois. The purpose of the study was to explore the time series properties of ground-water quality data collected at a relatively high sampling frequency. A secondary purpose was to determine the relative magnitudes of natural and sampling-related sources of variance in ground-water quality time series. The absence of this kind of information has severely hindered the design of ground-water sampling programs in the past.An autocorrelation analysis showed that the median sampling frequency for which the predicted ratio of effective independent sample size to total sample size was 0.5 (50% sampling redundancy) ranged from 6 to 14 samples per year. For a predicted ratio of effective independent sample size to total sample size of 0.9 (10% sampling redundancy) the sampling frequency ranged from 3 to 6 samples per year. This suggests that, for the wells sampled, sampling frequencies much higher than monthly can result in considerable loss of information, and may not be cost effective. Care was taken in the design of the field and laboratory sampling protocol to minimize the effects of measurement error. The data analysis confirmed that this goal was accomplished. In most cases considerably less than five percent of the total variability could be attributed to sampling and analytical error. Because of the relatively short duration of the study (42 biweekly sampling occasions at most wells) it was not possible to identify the magnitude of seasonal variations reliably.     

True and false positive rates in maximum contaminant level tests

The U.S. Environment Protection Agency (EPA) is promulgating a revised national primary drinking water regulation (NPDWR) which includes a monthly sample size and maximum contaminant level (MCL) for total coliform bacteria in public water systems. No previous quantification has been made of the coliform content that must be present in the sampled water in order for an MCL to be exceeded. This paper presents a method for evaluating the coliform level an MCL will detect with likelihood P.Our approach is to treat an MCL as a decision rule, with Type I (false positive) and Type II (false negative) error rates. The stringency of an MCL is quantified as the mean coliform level in the sampled system that it will detect with likelihood P. MCLs are contrasted on stringency by comparing the mean coliform level each targets for detection, with fixed error rates.Interim rules (NIPDWR), in effect since 1975, are shown to vary widely on the coliform content each targets for detection, that is, on stringency. Yes/no decisions on contamination have not been decided based on mean coliform content. Coliform levels permitted in monitored public water systems have been determined by the particular MCL used for testing. The same coliform level will test positively with one MCL 90 times in 100 yet be guaranteed 95% nondetection by a second MCL.EPA's reasonably safe standard for drinking water is reformulated on our stringency criteria. Its proposed monthly MCL is evaluated on its capability for maintaining this standard. Smaller systems will not provide its users this level of protection under the new rule.In addition, our evaluation of the safe water standard on stringency and the rationale for a monthly MCL require that coliform levels be identically distributed (i.d.) across month and sampled system. Empirical data strongly refute this model and question the utility of a monthly MCL.This work suggests an alternative, single sample MCL, with repeat sampling for verification, which can be configured to provide monitoring to discover mean coliform values at any level, in any size of system, at minimal extra cost.     

淮南市秋季大气可吸入颗粒物中多环芳烃的污染特征分析

2007年秋季在淮南市五个采样点采集大气可吸入颗粒物样品,用色谱-质谱法分析多环芳烃中16种优控污染物.结果显示,交通区PAHs浓度最高;PAHs以四环为主,二环所占比例最小;PM10与ΣPAHs成显著正相关关系,与苯并[a]芘成显著正相关;采用比值法对准南市PM10中的PAHs进行来源分析,得到PAHs主要来源于交通源及燃煤排放.     

Nitrate occurrence in the groundwater of the Loukkos perimeter

This study assesses the occurrence of nitrate in the groundwater beneath the R'mel area of the Loukkos perimeter (north-west Morocco), which covers an approximate area of 2,560 km2 and is located between the towns of Ksar el Kebir and Larache. It also borders the Atlantic Ocean. Groundwater supplies are the principal source of drinking water in this region and there is no public drinking water network in the rural area. This perimeter has a population of about 500,000 inhabitants of which the rural population represents 60%, many of whom have depended on and used the water from the aquifers for many years. The inhabitants and farmers depend on the groundwater supplies for drinking water, crop irrigation and other uses. The plain provides the ideal conditions for agriculture and the use of chemical fertilisers has been increasing. In this study, 53 water samples were collected from wells and springs. Each well or spring was sampled once or twice during 1998-2000. Nitrate concentrations ranged from extremely low up to 144 mg L(-1). Nitrate concentrations exceeded the maximum contaminant level (MCL) of 50 mg L(-1) in 12 of the 53 groundwater samples (23%), whereas 31 of the 53 samples (58%) had nitrate concentrations of less than 25 mg L(-1).     

Sewage contamination of a densely populated coral 'atoll' (Bermuda)

Bermuda is a densely populated coral 'atoll' located on a seamount in the mid-Atlantic (Sargasso Sea). There is no national sewerage system and the ～20 × 10(6)?L of sewage generated daily is disposed of via marine outfalls, cess pits/septic tanks underneath houses and through waste disposal (injection) wells. Gastrointestinal (GI) enterococci concentrations were measured in surface seawater samples collected monthly at multiple locations across the island over a 5-year period. According to the EU Bathing Water Directive microbial classification categories, 18 of the sites were in the 'excellent' category, four sites in the 'good', five sites were in the 'sufficient' and three sites in the 'poor' categories. One of the sites in the 'poor' category is beside a popular swimming beach. Between 20-30% of 58 sub tidal sediment samples collected from creeks, coves, bays, harbours and marinas in the Great Sound complex on the western side of Bermuda tested positive for the presence of the human specific bacterial biomarker Bacteroides (using culture-independent PCR-based methods) and for the faecal biomarker coprostanol (5β-cholestan-3-β-ol, which ranged in concentration from <0.05-0.77?mg?kg(?-?1). There was a significant statistical correlation between these two independent techniques for faecal contamination identification. Overall the microbial water quality and sedimentary biomarker surveys suggest sewage contamination in Bermuda was quite low compared with other published studies; nevertheless, several sewage contamination hotpots exist, and these could be attributed to discharge of raw sewage from house boats, from nearby sewage outfalls and leakage from septic tanks/cess pits.     

超高效液相色谱法测定土壤中微量阿特拉津

采用超高效液相色谱仪,建立了土壤中微量阿特拉津的快速检测方法.研究结果表明:采用反相C18色谱柱,以甲醇/水(70:30,v/v)为流动相,流速为0.2 ml/min,柱温为30℃,检测波长为220 nm条件下,在12.5～1000μg/L质量浓度范围内线性关系良好(r=0.9999),检出限0.18×10-3 mg/...     

Quantifying sample biases of inland lake sampling programs in relation to lake surface area and land use/cover

We quantified potential biases associated with lakes monitored using non-probability based sampling by six state agencies in the USA (Michigan, Wisconsin, Iowa, Ohio, Maine, and New Hampshire). To identify biases, we compared state-monitored lakes to a census population of lakes derived from the National Hydrography Dataset. We then estimated the probability of lakes being sampled using generalized linear mixed models. Our two research questions were: (1) are there systematic differences in lake area and land use/land cover (LULC) surrounding lakes monitored by state agencies when compared to the entire population of lakes? and (2) after controlling for the effects of lake size, does the probability of sampling vary depending on the surrounding LULC features? We examined the biases associated with surrounding LULC because of the established links between LULC and lake water quality. For all states, we found that larger lakes had a higher probability of being sampled compared to smaller lakes. Significant interactions between lake size and LULC prohibit us from drawing conclusions about the main effects of LULC; however, in general lakes that are most likely to be sampled have either high urban use, high agricultural use, high forest cover, or low wetland cover. Our analyses support the assertion that data derived from non-probability-based surveys must be used with caution when attempting to make generalizations to the entire population of interest, and that probability-based surveys are needed to ensure unbiased, accurate estimates of lake status and trends at regional to national scales.     

高效液相方法同时测定地表水中的阿特拉津和甲萘葳

主要研究用反相高效液相色谱法同时测定水样中的阿特拉津和甲萘葳。结果表明,低浓度水样：可取500ml,加入5%的氯化钠,经一定量的二氯甲烷萃取、浓缩、甲醇定容后,上机测定;高浓度水样：可将水样过滤后直接进样测定。该方法的阿特拉津和甲萘葳检出限分别为0.006μg/L和0.036μg/L,加标回收率分别可达74.2%~11...     

胶团强化超滤处理水中阿特拉津的研究

采用胶团强化超滤去除水中阿特拉津.考察了表面活性剂、pH、操作压力、操作时间以及温度对阿特拉津去除效果的影响.结果表明,胶团强化超滤法能有效去除水中阿特拉津,最佳工艺条件为:采用分子量为5 000 Dalton的聚砜中空纤维膜、SDBS浓度为8.00mmol/L、压力为0.15 MPa、pH为10、温度为25℃.在此条...     

Analysis of diazinon monitoring data from the Sacramento and Feather River watersheds: 1991-2001

The objectives of this study were to: (1) analyzehistorical diazinon water column monitoring data frominconsistent monitoring programs in mainstem and tributary sitesin the Sacramento and Feather River watersheds from 1991 to 2001to assess possible spatial and temporal trends and (2) determinethe probability of measured diazinon concentrations by site orsimilar pooled sites exceeding various proposed effectsbenchmarks such as Water Quality Criteria and 10th centilesderived from species sensitivity distributions proposed as targetconcentrations for Total Maximum Daily Loads (TMDLs). An analysisof diazinon monitoring data from both fixed and rain eventsampling from the Sacramento/Feather River watersheds from 1991to 2001 showed that 90th centiles for 27 different mainstemand tributary sites ranged from 12 to 14,897 ng L^-1. The 90th centiles were generally higher at tributary sites (as compared to mainstem sites) during rain event sampling prior to 1995. A comparison of rain event samples for similar sites sampled in 1994 and 2000 showed that 90th centiles were lower in seven of eight sites in 2000. A comparison of pooled mainstemsites between 1994 and 2000 for rain event data showed a lower90th centile value for 2000; 90th centiles were alsolower in 2000 at all pooled tributary sites and all sites whendata from a highly influential site was removed. For varioussite designations (all sites, pooled mainstem sites etc.) theprobability of exceeding the acute and chronic diazinon targetsdeveloped by California Department of Fish and Game decreasedfrom 1994 to 2000. These data clearly show progress in the 6 yrperiod in reducing environmental concentrations of diazinon.Probability of exceeding the 10th centile targets based onspecies sensitivity distributions for arthropods (the mostsensitive taxa to diazinon exposure) was similar and fairly lowbetween years; the highest percent probability of exceedance forany site designation was 20%.Results from a two-way ANOVA using individual measurementsfrom all sites sampled showed a significant decrease during rainevents between 1994 and 2000, although the decrease was notequivalent for all sites. Sources of uncertainty identified inthe analysis of rain event data from 1994 and 2000 wereinconsistent frequency of sampling during rain events for eachyear, unknown definition of rain events between the two years andnon-defined measurement point within the hydrograph of rainevents sampled in each year. Analysis of diazinon trends fromfixed sampling was limited due to lack of yearly data by site;therefore, only parametric analysis could be conducted. Based onparametric analysis of diazinon monitoring data from fixedsampling sites, the percent detected concentrations were greaterthan 20% for 12 tributary sites and 5 mainstem sites fromsamples collected during January-March. On the average over allsites and months, diazinon concentrations have decreased at fixedsampling sites in the Sacramento/Feather River watershed from1991 to 2001.     

Removal of atrazine and four organophosphorus pesticides from environmental waters by diatomaceous earth-remediation method

A new viable remediation technique based on the use of diatomaceous earth is proposed to improve the ecological system. Its ability to remove atrazine and the four organophosphorus pesticides parathion-methyl, chlorpyriphos, fenamiphos and methidathion from river and waste waters has been proven. A series of experiments including variable conditions, such as temperature, pH, contact time, pesticide concentration and adsorbent quantity, were performed to demonstrate the efficiency of pesticide removal from three different water samples. The batch experiments showed that diatomaceous earth was able to remove 95% of chlorpyriphos, 75% of methidathion and parathion-methyl and 55% of atrazine and fenamiphos from all types of waters tested. The individual adsorption of each pesticide on diatomaceous earth could be described by the Freundlich isotherm and a tentative adsorption mechanism was proposed. The Freundlich coefficient (Kf) and Freundlich constant (1/n) appeared to be closely related to the physicochemical properties (Kow, solubility) of the compounds. The actual results support the conclusion that diatomaceous earth has the potential to serve as an extractant in remediation techniques.     

固相萃取-高效液相色谱法测定水中呋喃丹、甲萘威和阿特拉津

采用固相萃取-高效液相色谱(SPE - HPLC)二极管阵列检测器同时测定水中呋喃丹、甲萘威和阿特拉津,以甲醇-水为流动相,采用梯度洗脱方式,选择220 nm为检测波长,二氯甲烷为洗脱剂.呋喃丹在0.200 mg/L ～5.00 mg/L、甲萘威和阿特拉津在0.020 mg/L～5.00 mg/L范围内线性良好,检出限...     

Concurrent Exposure Assessments of Atrazine and Metolachlor in the Mainstem, Major Tributaries and Small Streams of the Chesapeake Bay Watershed: Indicators of Ecological Risk

The goals of this study were to: (1) measure atrazine and metolachlor concentrations during both high and low use periods in the Chesapeake Bay's mainstem/major tributaries, smaller tributaries and representative small agricultural streams during 1995 and 1996; (2) compare these exposure data with toxicity benchmarks for each herbicide to predict ecological risk and (3) use in-stream fish community data collected in the streams to provide supportive data for ecological risk characterization. Spatially, atrazine (<0.10–98 g/L) and metolachlor (<0.10–68 g/L) concentrations were highest in the streams, followed by the small tributaries (<0.10–11 g/L atrazine; <0.10–8.6 g/L metolachlor) with the lowest concentration in the mainstem Bay/larger tributaries (<0.10–0.22 g/L atrazine; <0.10–0.24 g/L metolachlor). Temporally, concentrations of both herbicides were greatest in all three types of habitats in the late spring and early summer. Concentrations of atrazine and metolachlor were very low or non-detectable in all habitats sampled from early August to mid-April. Toxicity benchmarks of 20 g/L for atrazine based on an ecological No Observed Effect Concentration (NOEC) for microcosm/mesocosm studies and an acute 10th percentile of 53 g/L for metolachlor (protection of ninety % of the species) based on laboratory toxicity data were selected to assess annual and seasonal ecological risk. Both of these toxicity benchmarks were conservative estimates of ecological risk designed to protect the trophic group (plants) most sensitive to these herbicides. Based on a comparison of these toxicity benchmarks with two years of exposure data, the ecological risk from both atrazine and metolachlor exposure in the mainstem Chesapeake Bay/large tributaries, small tributaries and representative agriculturally dominated streams was generally judged to be low. During one 72-h stream rain event in 1995, the atrazine toxicity benchmark (20 g/L) was exceeded during part of the event. However, long-term permanent ecological effects are not expected based on the documented recovery potential of the most sensitive trophic group (plant communities) to the concentrations of atrazine reported and the transient nature of the atrazine pulses. Fish communities at the stream sites receiving the highest concentrations of both herbicides were judged to be healthy based on an Index of Biotic Integrity (IBI) developed for Maryland's coastal plain.     

曲线拟合对空气污染物浓度的预测

通过对深圳市1991年－2000年环境空气中SO2浓度月均值，年均值变化规律的分析，得出了其数学表达式所需的函数特征，建立了曲线拟合方程，并通过实例计算及一系列统计回归检验，表明SO2浓度的月均值、年均值实际变化与拟合曲线结果基本一致。     

A spatial analysis of pit latrine density and groundwater source contamination

This study aims to assess the relationship between chemical and microbial contamination of groundwater sources and a range of potential hazards in two peri-urban areas of Kisumu, Kenya where shallow wells and pit latrines are widely used. From 1998 to 2004, 263 samples were taken from 61 groundwater sources and tested for thermotolerant coliforms. Eighteen of these sources were also tested for chemical contaminants, including nitrate, chloride and fluoride. The locations of all water sources, buildings and pit latrines in the study area were surveyed. Local pit latrine densities were calculated using a geographic information system. Ten out 18 samples were above the World Health Organization guideline values for nitrate, 236 out of 263 were positive for thermotolerant coliforms, and all were above the guideline values for fluoride. There was neither a relationship between thermotolerant coliform levels and daily rainfall patterns nor with sanitary risk inspection scores for samples from shallow wells (r?=?0.01, p?=?0.91, n?=?191). The density of pit latrines within a 100-m radius was significantly correlated with nitrate and chloride levels (r?=?0.64, p?=?0.004 and r?=?0.46, p?=?0.05, respectively) but not with thermotolerant coliforms (r?=?0.22, p?=?0.11). These results illustrate both the public health risks associated with shallow groundwater sources, on-site sanitation and high population density. These findings have implications for current policies that promote latrine construction, especially in peri-urban areas of high population density. More comprehensive studies of larger communities should be commissioned to extend this analysis of the links between latrine density and groundwater contamination and so identify the contingent policy risks.     

On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters

A simple on-line method was developed for the analysis of pharmaceuticals, pesticides and some metabolites in drinking, surface and wastewater samples. The technique is based on the use of on-line solid-phase extraction combined with liquid chromatography electrospray tandem mass spectrometry with positive electrospray ionization (LC-ESI(PI)-MS/MS). The injection of only 1 mL of filtered water sample is used with a total analysis time of 20 min, including the period required to flush the SPE cartridge with organic solvent and reconditioning the LC column. Method detection limits were in the range of 2 to 24 ng L(-1) for the compounds of interest, with recoveries from 87 to 110% in surface as well as wastewater samples. Matrix effects were observed for some compounds without exceeding more than 25%. All results displayed a good degree of reproducibility, with relative standard deviations (RSD) of less than 12% for all compounds. Moreover, at least 200 samples were analyzed without altering the performance of the pre-concentration column. This method was preferred over traditional off-line procedures because it minimizes tedious sample preparation, increases productivity and sample throughput. The analysis of various water and wastewater samples showed that caffeine, carbamazepine and atrazine could be detected in all the samples analysed and the selected compounds are always present in at least one of the sample types.     

A comparison of techniques to sample salamander assemblages along highland streams of Maryland

Amphibians may be useful indicators of biological condition in small streams so determining which sampling technique maximizes encounters at the least cost and at the optimal time of year is important. Area constrained surveys (ACS), used by the Maryland Biological Stream Survey, were tested against cover board surveys, drift fences with pitfall and funnel traps, quadrat leaf litter searches, and leaf litter bags. Sixteen, 100 m-long sites were established in headwater streams in the Savage River State Forest in Garrett County, Maryland. Each technique was randomly assigned to a 25 m stream section within each overall sampling site, and sites were sampled once each month from May to October (2005) with additional sampling in March and April (2006). Area constrained surveys yielded means of 2.7 taxa and 14.9 total individuals per sampling visit, which was significantly higher than the yield of all other methods in all months except October and March, when yields were low for all techniques. Area constrained surveys were also significantly more cost-effective per taxon and per individual compared to all other methods. September produced the most taxa and individuals, October and March produced the least, and yields for April through August were similar to September. We employed removal sampling at four sites in April 2006, but abundance could not be estimated because a significant linear decrease in the accumulated catch versus catch per unit effort did not occur for three of the sites.     

Atrazine Transport Within a Coastal Zone in Southeastern Puerto Rico: a Sensitivity Analysis of an Agricultural Field Model and Riparian Zone Management Model

Agrichemical runoff from farmland may adversely impact coastal water quality. Two models, the Agricultural Policy/Environmental eXtender (APEX) and the Riparian Ecosystem Management Model (REMM), were used to evaluate the movement of the herbicide atrazine to the Jobos Bay National Estuarine Research Reserve from adjacent fields. The reserve is located on Puerto Rico’s southeast coast. Edge-of-field atrazine outputs simulated with the APEX were routed through a grass-forest buffer using the REMM. Atrazine DT₅₀ (half-life) values measured in both field and buffer soils indicated that accelerated degradation conditions had developed in the field soil due to repeated atrazine application. APEX simulations examined both the measured field and buffer soil atrazine DT₅₀ and the model’s default value. The use of the measured field soil atrazine degradation rate in the APEX resulted in 33 % lower atrazine transport from the field. REMM simulations indicated that the buffer system had the potential to reduce dissolved atrazine transport in surface runoff by 77 % during non-tropical storm events by increasing infiltration, slowing transport, and increasing time for pesticide degradation. During a large runoff event due to a tropical storm that occurred close to the time of an atrazine application, the REMM simulated only a 37 % reduction in atrazine transport. The results indicate that large storm events soon after herbicide application likely dominate herbicide transport to coastal waters in the region. These results agree with water quality measurements in the reserve. This study demonstrated the sensitivity of these models to variations in DT₅₀ values in evaluating atrazine fate and transport in the region and emphasizes that the use of measured DT₅₀ values can improve model accuracy.