Insights to false positive total cyanide measurements in wastewater plant effluents.

Many publicly owned treatment works in North America are exceeding permitted limits for total cyanide in their wastewater treatment effluents. A recently introduced rapid, segmented, flow-injection analysis procedure using UV digestion and amperometric detection of the membrane-separated cyanide was used to investigate the various scenarios by which elevated cyanide levels might be present in wastewater treatment plant effluent. A number of significant interferences can produce false positive bias during sample analysis with the traditional acid distillation technique, but are minimized or absent with the new analytical method. However, increased levels of cyanide were found in some chlorinated wastewaters compared to the levels before chlorination, suggesting a fast reaction mechanism associated with the disinfectant and some precursor in the wastewater. In particular, the contact of chlorine with nitrite in the presence of a carbon precursor appears to contribute to cyanide formation during wastewater treatment and sample handling. This paper explores the scenarios under which cyanide can form during wastewater treatment as well as those in which a false bias for total cyanide can be obtained during sample processing and provides guidance for appropriate sample handling, screening, and processing to ensure valid analytical results.     

A remote in situ monitor based on continuous flow analysis for the quantitation of sub-micromolar levels of hexavalent chromium in natural waters

We describe the design, optimization, and application of a small, lightweight, deployable monitoring instrument for accurately measuring parts-per-billion levels of hexavalent Cr in surface waters at hourly intervals. The monitor quantifies Cr(vi) using a standard molecular absorbance spectroscopic method, i.e. by formation of a complex with 1,5-diphenylcarbazide (DPC). The continuous flow analysis (CFA) design uses narrow conduits (0.90 mm) that are hot-forged onto poly(methyl methacrylate) ('Plexiglas') plates based on the method of Jannasch et al.(Anal. Chem., 1994, 66, 3352). The sample stream is drawn through the manifold at 25 microl min(-1) using a mini-peristaltic pump; osmotic pumps (10 microl h(-1)) are used to continuously inject reagent (2.0 mM DPC, 0.60 M HNO(3), 5.0% w/v acetone, and 0.10% w/v Brij-35) and to periodically introduce quality control standards and a cleaning solution (0.50 M HNO(3)). The 'Z-type' optical cell uses a liquid-core waveguide (10 mm) to collimate the light-emitting diode source beam (lambda(max) 574 nm) to a broadband photodiode detector. Figures of merit are: 7 min cycle time, response within 28 min and clear-down within 31 min, low waste generation (<40 ml d(-1)), detection limit (3sigma) of 48.4 microg l(-1) as Cr(vi) or 0.411 microM as chromic acid, 1.54% relative standard deviation at 100 microg l(-1), and selectivity for dissolved Cr(vi) in authentic surface water samples containing moderate levels (>0.21% w/v) of total particulate matter. Using a test chamber containing Milwaukee Harbor water that was periodically fortified with Cr(vi) standards, continuous testing over a 15 day period (354 h) yielded results that were in excellent agreement (<5% variation) with measurements made using an ICP-MS reference method. Drift in the calibration model over the test period was 1.23% and the variation in a 0.50 mg l(-1) Cr(vi) standard was 3.8%(n= 11). Known interferences to the DPC chemistry (Mo, V, and Hg at >5 mg l(-1)) were undetected in the harbor water by ICP-MS.     

Role of Patch Size, Disease, and Movement in Rapid Extinction of Bighorn Sheep

Abstract: The controversy (  Berger 1990, 1999 ; Wehausen 1999 ) over rapid extinction in bighorn sheep ( Ovis canadensis ) has focused on population size alone as a correlate to persistence time. We report on the persistence and population performance of 24 translocated populations of bighorn sheep. Persistence in these sheep was strongly correlated with larger patch sizes, greater distance to domestic sheep, higher population growth rates, and migratory movements, as well as to larger population sizes. Persistence was also positively correlated with larger average home-range size ( p = 0.058, n = 10 translocated populations) and home-range size of rams ( p = 0.087, n = 8 translocated populations). Greater home-range size and dispersal rates of bighorn sheep were positively correlated to larger patches. We conclude that patch size and thus habitat carrying capacity, not population size per se, is the primary correlate to both population performance and persistence. Because habitat carrying capacity defines the upper limit to population size, clearly the amount of suitable habitat in a patch is ultimately linked to population size. Larger populations (250+ animals) were more likely to recover rapidly to their pre-epizootic survey number following an epizootic ( p = 0.019), although the proportion of the population dying in the epizootic also influenced the probability of recovery ( p = 0.001). Expensive management efforts to restore or increase bighorn sheep populations should focus on large habitat patches located ≥23 km from domestic sheep, and less effort should be expended on populations in isolated, small patches of habitat.     

Restoring Ecological Integrity in Highly Regulated Rivers: The Role of Baseline Data and Analytical References

The goal of restoring ecological integrity in rivers is frequently accompanied by an assumption that a comparative reference reach can be identified to represent minimally impaired conditions. However, in many regulated rivers, no credible historical, morphological or process-based reference reach exists. Resilient restoration designs should instead be framed around naturalization, using multiple analytical references derived from empirically-calibrated field- and model-based techniques to develop an integrated ecological reference condition. This requires baseline data which are rarely collected despite increasing evidence for systematic deficiencies in restoration practice. We illustrate the utility of baseline data collection in restoration planning for the highly fragmented and regulated lower Merced River, California, USA. The restoration design was developed using various baseline data surveys, monitoring, and modeling within an adaptive management framework. Baseline data assisted in transforming conceptual models of ecosystem function into specific restoration challenges, defining analytical references of the expected relationships among ecological parameters required for restoration, and specifying performance criteria for post-project monitoring and evaluation. In this way the study is an example of process-based morphological restoration designed to prompt recovery of ecosystem processes and resilience. For the Merced River, we illustrate that project-specific baseline data collection is a necessary precursor in developing performance-based restoration designs and addressing scale-related uncertainties, such as whether periodic gravel augmentation will sustain bed recovery and whether piecemeal efforts will improve ecological integrity. Given the numerous impediments to full, historical, restoration in many river systems, it seems apparent that projects of naturalization are a critical step in reducing the deleterious impacts of fragmented rivers worldwide.