MODIFYING AUTOMATED PUMPING SAMPLERS FOR USE IN SMALL MOUNTAIN STREAMS1

ABSTRACT: Two modifications to automated pumping samplers improve discrete sampling during high flow events in small mountain streams. One modification entails mounting the intake nozzle on a bent, free-swinging metal rod supported in midstream. This allows sampling in midstream yet prevents the buildup of floatable organic debris that otherwise would cause the intake to fail. On the lower end of the rod, dynamic forces exerted by the stream keep the intake submerged over diverse flow conditions. The second modification consists of a magnetic switching device that automatically activates the pumping sampler at any preset stage on the rising limb of a storm hydrograph. The pumping sampler then remains on to collect one sample per hour which allows field crews sufficient time to change bottles before the sampler fills its 28-bottle capacity. This device improves the capability to sample frequently at fixed intervals, yet with minimal maintenance between runoff events. It also ensures sample collection during the rising limb of the hydrograph when flow and sediment concentrations are rapidly changing. Both modifications have improved data collection during periods of storm runoff.     

MAGNETIC TRIGGER FOR AUTOMATIC PUMPING SAMPLERS1

ABSTRACT: A stage-activated triggering device was developed for automatic pumping samplers. The device consists of a proximity switch and ten magnets mounted radially at equal intervals on a plexiglass disk. The triggering device allows discrete sampling of stream water at 3.0 cm intervals of stage. The trigger proved dependable during two years of use at three headwater streams in the Ouachita Mountains of southeastern Oklahoma.     

A DIGITAL CONTROLLER FOR DISCRETE STAGE ACTIVATION OF AUTOMATIC PUMPING SAMPLERS1

ABSTRACT: An electronic controller was developed to facilitate water sampling at discrete stage heights in perennial mountain streams of southeast Oklahoma. The controller operates in conjunction with an automatic pumping sampler and a magnetic, relay transducer. In response to changes in stage, the transducer generates an electrical pulse when relays are closed by a magnetic float. The controller monitors these relay closures and signals the sampler to pump a single sample at each desired water level during both rising and falling stages. After a sample is taken, additional switch closures at that stage axe ignored until the relay immediately above or below is closed. Inadvertent switch closures caused by turbulent stage fluctuations are not translated to the sampler thus eliminating duplicate or multiple samples at a given stage. Field testing has proven this device to be a reliable component with a range of applications for improving water quality sampling systems. The controller features battery operation, low power consumption, circuit simplicity and can be easily constructed for less than $100, including parts and labor.     

Transport of gellan gum microbeads through sand: an experimental evaluation for encapsulated cell bioaugmentation

Transport of 10-40 microm gellan gum microbeads was studied in horizontal sand columns to evaluate the feasibility of using gel-encapsulated bacteria for bioaugmentation of contaminated aquifers. Three 5.2 x 110 cm columns were packed with sand (column A: 0.5-2 mm, column B: 0.25-2 mm, and column C: 0.125-2 mm). Microbeads in artificial groundwater were injected at 0.5 l h(-1) during intermittent 12-h periods. Breakthrough of microbeads increased with injection time, varying as a descending function of travel distance. After 72 h of injection, about 75% of injected microbeads were dispersed across a 5-110 cm distance from the inlet in column A, compared to 78% across a 5-50 cm in column B, and 76% across a 5-20 cm in column C. The wider dispersion of microbeads across the length of column A, compared to those observed in columns B and C, suggests a higher potential for the formation of a uniform bioactive zone of encapsulated cells across a sandy aquifer with such grain size distribution and hydrodynamic properties.     

Greenhouse gases in non-oxygenated and artificially oxygenated eutrophied lakes during winter stratification

Concentrations of dissolved methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O) were measured in the water columns of non-oxygenated and artificially oxygenated, ice-covered eutrophied lakes in the mid-boreal zone in Finland during late winter 1997 and 1999. Sampling was conducted during winter stratification, the critical period for oxygen (O2) deficiency in seasonally ice-covered, thermally stratified lakes. Oxygen concentrations were maintained at least at a moderate level throughout the oxygenated water columns, whereas the non-oxygenated columns suffered anoxic hypolimnia. The mean concentrations of dissolved CH4 exceeding the atmospheric equilibrium were greater in the non-oxygenated water columns (20.6-154 microM) than in the oxygenated ones (0.01-1.41 microM). In contrast, the mean excess CO2 concentrations varied less between the non-oxygenated and oxygenated sites (0.28-0.47 and 0.25-0.31 mM, respectively). Oxygenated water columns had greater mean excess concentrations of N2O (0.018-0.032 microM) than the non-oxygenated ones (0.005-0.024 microM). If the accumulated greenhouse gas stores in the water columns during winter are assumed to be released to the atmosphere during the spring overturn, the global warming potentials (GWP, time horizon 100 yr) of these potential emissions at the non-oxygenated, eutrophic study sites ranged from 177 to 654 g CO2 equivalent (CO2-e) m-2 compared with 144 to 173 g CO2-e m-2 at the oxygenated sites. The increase in the accumulation of CH4 was the main reason for the higher GWP of the non-oxygenated sites. Anthropogenic eutrophication of lake ecosystems can generate increased CH4 emissions due to associated O2 depletion of their sediment and water column.     

SAMPLING STRATEGIES FOR ESTIMATING ACUTE AND CHRONIC EXPOSURES OF PESTICIDES IN STREAMS1

ABSTRACT: The Food Quality Protection Act of 1996 requires that human exposure to pesticides through drinking water be considered when establishing pesticide tolerances in food. Several systematic and seasonally weighted systematic sampling strategies for estimating pesticide concentrations in surface water were evaluated through Monte Carlo simulation, using intensive datasets from four sites in northwestern Ohio. The number of samples for the strategies ranged from 4 to 120 per year. Sampling strategies with a minimal sampling frequency outside the growing season can be used for estimating time weighted mean and percentile concentrations of pesticides with little loss of accuracy and precision, compared to strategies with the same sampling frequency year round. Less frequent sampling strategies can be used at large sites. A sampling frequency of 10 times monthly during the pesticide runoff period at a 90 km² basin and four times monthly at a 16,400 km² basin provided estimates of the time weighted mean, 90^th, 95^th, and 99^th percentile concentrations that fell within 50 percent of the true value virtually all of the time. By taking into account basin size and the periodic nature of pesticide runoff, costs of obtaining estimates of time weighted mean and percentile pesticide concentrations can be minimized.     

Bacterial removal and protozoan grazing in biological sand filters

The objective of the study was to investigate the importance of protozoan predation as a biological removal mechanism in sand filters used for purification of bacteria from wastewater. Eleven sand filter columns were seeded with a high dose of wastewater (70 mm d(-1)) and a high concentration (10(8) colony forming units [CFU] mL(-1)) of Aeromonas hydrophila (American Type Culture Collection [ATCC] 14715) for a period of 30 d. Water samples from three filter outlets were analyzed for the concentration of A. hydrophila. In addition, one filter column was sacrificed each sampling day for the quantification of A. hydrophila, culturable bacteria (heterotrophic plate counts, HPC), total bacterial counts, and protozoa in the sand. The mean removal efficiency of A. hydrophila in the sand filter columns was 4.7 log units. The concentration of A. hydrophila in the sand filter effluent, however, had a clearly time-dependent pattern from high (log 6) and unstable concentrations to low and more stable levels (log 2). The removal efficiency of A. hydrophila correlated significantly (P = 0.0005, r2 = 0.6) with numbers of protozoa in the sand filters. Significantly higher (P < 0.05) concentrations of A. hydrophila were observed in sand filter effluents from columns treated with the protozoan inhibitor cycloheximide, compared with nontreated columns. Results from the present study show that protozoan grazing plays an important role as a bacterial removal mechanism in sand infiltration systems.     

Estimating upper percentiles of surface water monitoring data with sparse samples

The estimation of upper percentiles of chemical concentrations in surface water systems within sites and regions may be necessary for the assessment of potential risk to ecosystems and human health. Limited sample sizes at monitoring sites often limit the use of direct methods to estimate upper percentiles. In such cases, upper percentiles within regions within a time frame may be estimated by pooling data across sites and years, and then deriving percentile estimates from the pooled dataset. The method uses the observations resulting from either a known probability-sampling design or a sampling design treated like one because its observations come close to matching that of a probability-sample. These observations are then weighted to ensure that estimates are representative of a target population across all the sites within the region and the range of years in the time frame. This method of estimating upper percentiles of annual site concentration profiles is demonstrated using atrazine and validated using the monitoring data from both sparsely sampled and high-frequency water monitoring programs, where point and interval estimates of the 90th, 95th, and 99th pooled population percentiles are provided. This method shows that the pooled data from multiple sparse datasets can be used to provide estimates of near-peak concentrations with greater certainty, which are consistent with those generated by high-frequency sampling monitoring programs.     

蚕豆根细胞慧星试验对西河水诱变性检测

本文采用新建立的蚕豆根细胞慧星试验对南充市西河三个污染断面河水污染物的DNA损伤作用进行了监测。结果表明,所监测的三个点均存在较明显的诱变剂／致癌剂污染;新建立的蚕豆根细胞慧星试验的灵敏度足以直接检测水体环境致突变／致癌物的污染。     

Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

浮选柱用于油田回注水处理的研究

本文提出了处理含油污水的新型气浮设备─—浮选柱。在实验室装置上研究了其结构参数和操作参数对浮选性能的影响。研究结果表明：浮选柱是一种具有高效、节能等优点的含油污水处理装置，除油率在９０％左右，处理１ｍ３污水能耗为０．１１３ｋＷｈ，比从国外引进的ＷＥＭＣＯ充气浮选机能耗低５０％，成本仅为ＷＥＭＣＯ充气浮选机的１／５。本浮选柱已获得中国专利。     

PUBLIC PERCEPTIONS IN WATER QUALITY EVALUATION1

ABSTRACT: A Visual Perception Test, consisting of photographic slides of water sites, was designed to examine laymen's water quality perceptions. The slides were taken at five water sites where the level of visual pollution was artifically altered by the investigator. Analysis of variance indicated that the water sites were evaluated differently for each of five pollution levels. Increases in water discoloration and the quality of litter were viewed as increases in level of pollution. Laymen not only evaluated visually polluted sites lower for uses such as picnicking, but they also evaluated the quality of the actual water lower. Stepwise multiple regression indicated that a combination of water color, scenic beauty appreciation, quality of the surrounding environment and industry as a pollution source explained 73 percent of the variance in predicting Overall Pollution. Application of factor analysis simplified the variables to an Overall Pollution Factor and a Boating Use Factor.     

Enhanced biogeochemical cycling and subsequent reduction of hydraulic conductivity associated with soil-layer interfaces in the vadose zone

Biogeochemical dynamics in the vadose zone are poorly understood due to the transient nature of chemical and hydrologic conditions but are nonetheless critical to understanding chemical fate and transport. This study explored the effects of a soil layer on linked geochemical, hydrological, and microbiological processes. Three laboratory soil columns were constructed: a homogenized medium-grained sand, a homogenized organic-rich loam, and a sand-over-loam layered column. Upward and downward infiltration of water was evaluated during experiments to simulate rising water table and rainfall events, respectively. In situ collocated probes measured soil water content, matric potential, and Eh. Water samples collected from the same locations were analyzed for Br, Cl, NO, SO, NH, Fe, and total sulfide. Compared with homogeneous columns, the presence of a soil layer altered the biogeochemistry and water flow of the system considerably. Enhanced biogeochemical cycling was observed in the layered column over the texturally homogeneous soil columns. Enumerations of iron- and sulfate-reducing bacteria showed 1 to 2 orders of magnitude greater community numbers in the layered column. Mineral and soil aggregate composites were most abundant near the soil-layer interface, the presence of which likely contributed to an observed order-of-magnitude decrease in hydraulic conductivity. These findings show that quantifying coupled hydrologic-biogeochemical processes occurring at small-scale soil interfaces is critical to accurately describing and predicting chemical changes at the larger system scale. These findings also provide justification for considering soil layering in contaminant fate and transport models because of its potential to increase biodegradation or to slow the rate of transport of contaminants.     

TRENDS IN LEAD CONCENTRATIONS IN MAJOR U.S. RIVERS AND THEIR RELATION TO HISTORICAL CHANGES IN GASOLINE-LEAD CONSUMPTION1

ABSTRACT: Declines in concentrations of dissolved lead occurred at nearly two-thirds of 306 locations on major U.S. rivers from 1974 to 1985. Declines in dissolved lead concentrations are statistically significant (p < 0.10) at approximately one-third of the sampling locations. Statistically significant increases in dissolved lead concentrations occurred at only 6 percent of the sites, but are clustered in the Texas-Gulf and Lower Mississippi regions. Possible explanations for the observed trends in lead concentrations are tested through comparisons with (1) records of lead discharges from major sources including leaded-gasoline consumption and municipal- and industrial-point source discharges, (2) trends in various water-quality constituents such as pH and total alkalinity, and (3) basin characteristics such as drainage area. Statistically significant declines in lead concentrations in streams and gasoline lead (i.e., the largest source of lead at these sites) are highly coincident for the 1979 to 1980 period at most sampling locations. The greatest amount of decline in gasoline lead occurred at sites showing statistically significant downtrends in stream concentrations of lead from 1974 to 1985. No more than 5 percent of the trends in stream lead are influenced by municipal- and industrial-point sources of lead. Factors that affect the transport of dissolved lead, including lead solubility, suspended sediment, and basin characteristics such as drainage basin size, are not significantly related to trends in dissolved lead. Trends in streamflow explain no more than 7 percent of the downtrends in concentrations of lead and may partly explain the frequent increases in lead concentrations in the Texas-Gulf and Lower Mississippi regions.     

ATRAZINE IN SPRING RUNOFF AS RELATED TO ENVIRONMENTAL SETTING EBRASKA, 19921

ABSTRACT: A synoptic sampling of five surface-water sites in central Nebraska was conducted by the U.S. Geological Survey as part of its National Water-Quality Assessment Program during storm runoff in May 1992 to relate transport, yields, and concentrations of atrazine to environmental setting. Atrazine was the most extensively applied pesticide in the study unit. Atrazine transport was related to the size of contributing drainage area, quantity of atrazine applied, amount of precipitation, and volume of stream-flow. Estimated yields and mean concentrations of atrazine were related to the percentage of cropland in a drainage area. The largest estimated yields and mean concentrations of atrazine in surface water were associated from drainage areas with the highest percentage of cropland, and the smallest was associated with the smallest amount of cropland. Atrazine concentrations increased as streamflow increased but decreased at or near the time of peak streamflows, perhaps due to dilution. Atrazine concentrations then increased and remained elevated far into the stream recession. Atrazine is a regulated contaminant in finished public-water supplies. Large concentrations of atrazine could affect the management of public-water supplies because atrazine remains in solution in contrast to many other pesticides that are more easily removed.     

A transport model with coupled ternary exchange and chemisorption retention for hydrazinium cations

A numerical model was developed to describe the fate and transport of hydrazinium (N2H5+) and competing Ca2+ and H+ cations applied in acidic solutions to columns of Ca2+/H+-saturated sandy soil during steady saturated flow conditions. Instantaneous ternary H+-Ca2+-N2H5+ cation exchange using the Gaines-Thomas approach was combined with second-order, irreversible, kinetic chemisorption of exchange-phase N2H5+ ions as major retention mechanisms for N2H5+. Exchange-mediated chemisorption is assumed to occur as chemical binding of N2H5+ ions located on carboxyl-group exchange sites to nearby carbonyl groups, consequently decreasing the effective soil cation exchange capacity (CEC). Comparison of simulated and observed breakthrough curves (BTCs) for concentrations of N2H5+ and Ca2+ ions in column effluent was used in model evaluation. The cation transport model with cation exchange coupled with exchange-mediated chemisorption provided a valid first approximation for N2H5+ transport.     

Time series in M dimensions: The one-dimensional case: Pollution in the Chicago Sanitary and Ship Canal

A nonstationary time-series model is used to examine the changes occurring at sampling stations on the Chicago Sanitary and Ship Canal. Using data from upstream sampling sites, downstream levels of dissolved oxygen, total dissolved solids, nitrates and nitrites, and ammonia are accurately predicted. The method is simple, insensitive to extreme values, and responsive to changes in the system.     

Coupled cycles of dissolved oxygen and nitrous oxide in rivers along a trophic gradient in southern Ontario, Canada

Diel (24-h) cycling of dissolved O2 (DO) in rivers is well documented, but evidence for coupled diel changes in DO and nitrogen cycling has only been demonstrated in hypereutrophic systems where DO approaches zero at night. Here, we show diel changes in N2O and DO concentration at several sites across a trophic gradient. Nitrous oxide concentration increased at night at all but one site in spring and summer, even when gas exchange was rapid and minimum water column DO was well above hypoxic conditions. Diel N2O curves were not mirror images of DO curves and were not symmetrical about the mean. Although inter- and intrasite variation was high, N2O peaked around the time of lowest DO at most of the sites. These results suggest that N2O must be measured several times per diel period to characterize curve shape and timing. Nitrous oxide concentration was not significantly correlated with NO3- concentration, contrary to studies in agricultural streams and to the current United Nations Intergovernmental Panel for Climate Change protocols for N2O emission estimation. The strong negative correlation between N2O concentration and daily minimum DO concentration suggested that N2O production was limited by DO. This is consistent with N2O produced by nitrite reduction. The ubiquity of diel N2O cycling suggests that most DO and N2O sampling strategies used in rivers are insufficient to capture natural variability. Ecosystem-level effects of microbial processes, such as denitrification, are sensitive to small changes in redox conditions in the water column even in low-nutrient oxic rivers, suggesting diel cycling of redox-sensitive compounds may exist in many aquatic systems.     

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.     

Passive Samplers for NOx Monitoring: A Critical Review

Nitrogen oxide is an important gaseous air pollutant. It plays a major role in atmospheric chemistry, particularly in the formation of secondary air pollutants such as ozone, peroxyacyl nitrate (PAN), nitrate aerosols, and contributes to environmental acidification. A comprehensive assessment of NO₂ levels in the atmosphere is required for developing effective strategies for control of air pollution and improvement of air quality. Consequently, spatial NO₂ monitoring has become an important aspect of air quality assessment. Present NO₂ monitoring networks are mostly confined to urban areas, having a limited number of monitoring sites. Wide spatial NO₂ monitoring in India is constrained because of the limited availability of the monitoring equipment, such as continuous chemiluminesence monitors, high volume and handy samplers, which are expensive and need to be imported. Moreover, they require elaborate infrastructure, scientific personnel, technical support and uninterrupted power supply. In an effort to overcome the above shortcomings, passive samplers have been successfully used for large scale monitoring of NO₂ in the ambient environment.In recent years, passive samplers have been gaining increasing attention because they are simple, lightweight and cheap devices, which operate without any power source. Passive samplers have been found to be efficient, cost effective and free from the need for elaborate calibration and maintenance. Hence, they are ideally suited for developing a wide spatial network for NO₂ monitoring. This paper presents a comprehensive review including, historical development and critical assessment of validation studies along with comparison of both badge and tube type passive samplers. An attempt has been also made to highlight advantages and limitations, as well as discussion on the factors affecting the efficiency of passive samplers under field conditions.