Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Methods development and use of macroinvertebrates as indicators of ecological conditions for streams in the Mid-Atlantic Highlands Region

The Mid-Atlantic Highlands Assessment (MAHA) included the sampling of macroinvertebrates from 424 wadeable stream sites to determine status and trends, biological conditions, and water quality in first through third order streams in the Mid-Atlantic Highlands Region (MAHR) of the United States in 1993–1995. We identified reference and impaired sites using water chemistry and habitat criteria and evaluated a set of candidate macroinvertebrate metrics using a stepwise process. This process examined several metric characteristics, including ability of metrics to discriminate reference and impaired sites, relative scope of impairment, correlations with chemical and habitat indicators of stream disturbance, redundancy with other metrics, and within-year variability. Metrics that performed well were compared with metrics currently being used by three states in the region: Pennsylvania, Virginia, and West Virginia. Some of the metrics used by these states did not perform well when evaluated using regional data, while other metrics used by all three states in some form, specifically number of taxa, number of EPT taxa, and Hilsenhoff Biotic Index, performed well overall. Reasons for discrepancies between state and regional evaluations of metrics are explored. We also provide a set of metrics that, when used in combination, may provide a useful assessment of stream conditions in the MAHR.     

Comparison of macroinvertebrate sampling methods for nonwadeable streams

Bioassessment of nonwadeable streams in the United States is increasing, but methods for these systems are not as well-developed as for wadeable streams. In this study, we compared six macroinvertebrate field sampling methods for nonwadeable streams adapted from those used by three major programs: the U.S. Environmental Protection Agencys Environmental Monitoring and Assessment Program-Surface Waters, the U.S. Geological Surveys National Water Quality Assessment Program, and the Ohio Environmental Protection Agency, Division of Surface Water Biocriteria Program. We performed all six methods at 60 sites across four rivers and measured water chemistry and physical habitat at each site to assess abiotic conditon. Sites were divided into two groups: those influenced by navigational lock and dam structures (restricted flow, or RF) and those free-flowing or with lowhead dams (run-of-the-river, or ROR). Metrics based on passive Hester-Dendy artificial substrate samplers differed greatly from active sampling methods (i.e., using nets) but represented abiotic conditions well in both ROR and RF sites. Although metric values were similar across certain sampling methods, the metrics significantly correlated with abiotic variables varied among methods and between ROR and RF sites. These results emphasize that methods are not interchangeable, and the ability to detect certain stressors depends on sampling method.The U.S. Governments right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

An interlaboratory comparison of sediment elutriate preparation and toxicity test methods

Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.     

Assessment of wadeable stream resources in the driftless area ecoregion in Western Wisconsin using a probabilistic sampling design

The Wisconsin Department of Natural Resources (WDNR), with support from the U.S. EPA, conducted an assessment of wadeable streams in the Driftless Area ecoregion in western Wisconsin using a probabilistic sampling design. This ecoregion encompasses 20% of Wisconsin’s land area and contains 8,800 miles of perennial streams. Randomly-selected stream sites (n = 60) equally distributed among stream orders 1–4 were sampled. Watershed land use, riparian and in-stream habitat, water chemistry, macroinvertebrate, and fish assemblage data were collected at each true random site and an associated “modified-random” site on each stream that was accessed via a road crossing nearest to the true random site. Targeted least-disturbed reference sites (n = 22) were also sampled to develop reference conditions for various physical, chemical, and biological measures. Cumulative distribution function plots of various measures collected at the true random sites evaluated with reference condition thresholds, indicate that high proportions of the random sites (and by inference the entire Driftless Area wadeable stream population) show some level of degradation. Study results show no statistically significant differences between the true random and modified-random sample sites for any of the nine physical habitat, 11 water chemistry, seven macroinvertebrate, or eight fish metrics analyzed. In Wisconsin’s Driftless Area, 79% of wadeable stream lengths were accessible via road crossings. While further evaluation of the statistical rigor of using a modified-random sampling design is warranted, sampling randomly-selected stream sites accessed via the nearest road crossing may provide a more economical way to apply probabilistic sampling in stream monitoring programs.     

Electrofishing in boatable rivers: Does sampling design affect bioassessment metrics?

Data were collected from 60 boatable sites using an electrofishing design that permitted comparisons of the effects of designs and distances on fish assemblage metrics. Sites were classified a priori as Run-of-the-River (ROR) or Restricted Flow (RF). Data representing four different design options (i.e., 1000 and 2000 m for both single and paired banks) were extracted from the dataset and analyzed. Friedman tests comparing metric values among the designs detected significant differences for all richness metrics at both types of sites and for catch per unit effort and percent tolerant species at ROR sites. Richness metrics were generally higher for the two 2000-m designs than for the two 1000-m designs. When plotted against cumulative electrofishing distance, the percent change in metrics declined sharply within approximately 1000 m, after which metrics usually varied by less than 10%. These data demonstrate that designs electrofishing 1000 m of shoreline are sufficient for bioassessments on boatable rivers similar to those in this study, regardless of whether the shoreline is along a single bank or distributed equally among paired banks. However, at sites with depths greater than 4 m, it may be advisable to employ nighttime electrofishing or increase day electrofishing designs to 2000 m.The U.S. Governments right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Sampling effort needed to estimate condition and species richness in the Ohio river, USA

The level of sampling effort required to characterize fish assemblage condition in a river for the purposes of bioassessment may be estimated via different approaches. However, the goal with any approach is to determine the minimum level of effort necessary to reach some specific level of confidence in the assessment. In the Ohio River, condition is estimated and reported primarily at the level of pools defined by lock and dam structures. The goal of this study was to determine the minimum level of sampling effort required to adequately characterize pools in the Ohio River for the purpose of bioassessment. We followed two approaches to estimating required sampling effort using fish assemblage data from a long-term intensive survey across a number of Ohio River pools. First, we estimated the number of samples beyond which variation in the multimetric Ohio River Fish Index (ORFIn) leveled off. Then, we determined the number of samples necessary to collect approximately 90% of the fish species observed across all samples collected within the pool. For both approaches, approximately 15 samples were adequate to reduce variation in IBI scores to acceptable levels and to capture 90% of observed species in a pool. The results of this evaluation provide a basis not only for the Ohio River Valley Water Sanitation Commission (ORSANCO) but also states and other basin commissions to develop sampling designs for bioassessment that ensure adequate sampling of all assessment units.     

Development and evaluation of a Macroinvertebrate Biotic Integrity Index (MBII) for regionally assessing Mid-Atlantic Highlands Streams

The Macroinvertebrate Biotic Integrity Index (MBII) was developed from data collected at 574 wadeable stream reaches in the Mid-Atlantic Highlands region (MAHR) by the U.S. Environmental Protection Agency's (USEPA) Environmental Monitoring and Assessment Program (EMAP). Over 100 candidate metrics were evaluated for range, precision, responsiveness to various disturbances, relationship to catchment area, and redundancy. Seven metrics were selected, representing taxa richness (Ephemeroptera richness, Plecoptera richness, Trichoptera richness), assemblage composition (percent non-insect individuals, percent 5 dominant taxa), pollution tolerance [Macroinvertebrate Tolerance Index (MTI)], and one functional feeding group (collector-filterer richness). We scored metrics and summed them, then ranked the resulting index through use of independently evaluated reference stream reaches. Although sites were classified into lowland and upland ecoregional groups, we did not need to develop separate scoring criteria for each ecoregional group. We were able to use the same metrics for pool and riffle composite samples, but we had to score them differently. Using the EMAP probability design, we inferred the results, with known confidence bounds, to the 167,797 kilometers of wadeable streams in the Mid-Atlantic Highlands. We classified 17% of the target stream length in the MAHR as good, 57% as fair, and 26% as poor. Pool-dominated reaches were relatively rare in the MAHR, and the usefulness of the MBII was more difficult to assess in these reaches. The process used for developing the MBII is widely applicable and resulted in an index effective in evaluating region-wide conditions and distinguishing good and impaired reaches among both upland and lowland streams dominated by riffle habitat.     

Evaluation of an alternate method for sampling benthic macroinvertebrates in low-gradient streams sampled as part of the National Rivers and Streams Assessment

Benthic macroinvertebrates are sampled in streams and rivers as one of the assessment elements of the US Environmental Protection Agency’s National Rivers and Streams Assessment. In a 2006 report, the recommendation was made that different yet comparable methods be evaluated for different types of streams (e.g., low gradient vs. high gradient). Consequently, a research element was added to the 2008–2009 National Rivers and Streams Assessment to conduct a side-by-side comparison of the standard macroinvertebrate sampling method with an alternate method specifically designed for low-gradient wadeable streams and rivers that focused more on stream edge habitat. Samples were collected using each method at 525 sites in five of nine aggregate ecoregions located in the conterminous USA. Methods were compared using the benthic macroinvertebrate multimetric index developed for the 2006 Wadeable Streams Assessment. Statistical analysis did not reveal any trends that would suggest the overall assessment of low-gradient streams on a regional or national scale would change if the alternate method was used rather than the standard sampling method, regardless of the gradient cutoff used to define low-gradient streams. Based on these results, the National Rivers and Streams Survey should continue to use the standard field method for sampling all streams.