Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.     

Spatial and seasonal variations in atrazine and metolachlor surface water concentrations in Ontario (Canada) using ELISA

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 μg L⁻¹ (median = 0.12 μg L⁻¹) for atrazine and from <0.1 to 1.83 μg L⁻¹ (median = 0.09 μg L⁻¹) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 μg L⁻¹) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R² value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.     

NITRATE CONTAMINATION IN OREGON WELL WATER: GEOLOGIC VARIABILITY AND THE PUBLIC'S PERCEPTION1

ABSTRACT: Approximately 4.5 million people in the United States who rely on well water are exposed to nitrate‐N concentrations exceeding the 10 mg/l standard. In this study in the Southern Willamette Valley in Oregon we reassessed nitrate‐N in rural wells sampled in 2000–2001, compared nitrate‐N concentrations among geological units, and surveyed residents about their perceptions of well water quality. Nitrate‐N concentrations were again sampled in 2002 and found to have increased significantly from the previous period. With rapid population growth in the area, the potential health risk in drinking well water that exceeds 10 mg/l nitrate‐N warrants continued public education. Nitrate‐N concentrations were found to be higher in the Holocene alluvium of the Willamette River and the Pleistocene sand and gravel post‐Missoula Flood deposits. Researchers conducting future studies may choose to stratify and monitor wells by geologic unit and by other parameters that estimate input of nutrients to the environment. Opinions differed between agricultural landowners and nonagricultural landowners with regard to the impact that agricultural fertilizers may have on water quality. Participants were supportive of a range of regulatory actions that might be used by homeowners or landowners to address ground water contamination. Given that the area is now designated a Groundwater Management Area, understanding local stakeholders’perceptions is critical and strategic and has the potential to help public agencies manage potential conflicts of opinion among stakeholders, build consensus, and help guide the approach to restoring ground water quality.     

Prymnesium parvum: The Texas Experience1

Southard, Gregory M., Loraine T. Fries, and Aaron Barkoh, 2010. Prymnesium parvum: The Texas Experience. Journal of the American Water Resources Association (JAWRA) 46(1):14-23. DOI: 10.1111/j.1752-1688.2009.00387.x Abstract: Golden alga Prymnesium parvum was first identified in Texas during a fish kill investigation on the Pecos River in 1985. Since then golden alga kills occurred sporadically in a variety of waters in the western part of the state until 2001 when the alga became endemic in the Brazos, Canadian, Colorado, Red, and Rio Grande river systems, including the water supplies of two public fish hatcheries, the Possum Kingdom and Dundee state fish hatcheries. The increasing area adversely affected by the alga and frequent massive fish kills heightened public and political awareness and concerns regarding the ecological and economic impacts of P. parvum blooms. The Texas Parks and Wildlife Department (TPWD), the wildlife conservation agency of the state, responded to these concerns with a program to assess the ecological and economic impacts and to develop management options. To date 33 water bodies have been affected and losses are conservatively estimated at 34 million fish valued at US$13 million. Several sport fisheries, including smallmouth bass Micropterus dolomieu, striped bass Morone saxatilis, channel catfish Ictalurus punctatus, and blue catfish Ictalurus furcatus, have been severely affected. Additionally, 26 imperiled fish species occur in the affected water basins and some have been adversely affected. Economic losses associated with reduced fishing and other water-based recreational activities appear considerable. The combined economic losses to three counties (Palo Pinto, Stephens, and Young) surrounding Possum Kingdom reservoir for 2001 and 2003 were estimated at US$2.8 million and US$1.1 million, respectively. This paper describes how the TPWD responded to public and political concerns relative to the emergence of golden alga, its harmful effects to fisheries, and its historic and current statewide distribution.     

A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. The 25-mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37-mm filters. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

Modeling the costs and benefits of dam construction from a multidisciplinary perspective

Although the benefits of dam construction are numerous, particularly in the context of climate change and growing global demand for electricity, recent experience has shown that many dams have serious negative environmental, human, and political consequences. Despite an extensive literature documenting the benefits and costs of dams from a single disciplinary perspective, few studies have simultaneously evaluated the distribution of biophysical, socio-economic, and geopolitical implications of dams. To meet the simultaneous demands for water, energy, and environmental protection well into the future, a broader view of dams is needed. We thus propose a new tool for evaluating the relative costs and benefits of dam construction based on multi-objective planning techniques. The Integrative Dam Assessment Modeling (IDAM) tool is designed to integrate biophysical, socio-economic, and geopolitical perspectives into a single cost/benefit analysis of dam construction. Each of 27 different impacts of dam construction is evaluated both objectively (e.g., flood protection, as measured by RYI years) and subjectively (i.e., the valuation of said flood protection) by a team of decision-makers. By providing a visual representation of the various costs and benefits associated with two or more dams, the IDAM tool allows decision-makers to evaluate alternatives and to articulate priorities associated with a dam project, making the decision process about dams more informed and more transparent. For all of these reasons, we believe that the IDAM tool represents an important evolutionary step in dam evaluation.     

Conservation Opportunities for Securing In-Stream Flows in the Platte River Basin: A Case Study Drawing on Casper,Wyoming’s MunicipalWater Strategy

The Platte River Basin consists of tributaries largely in Wyoming, Colorado and Western Nebraska, with the main stem in Central Nebraska. Critical wildlife habitat on the main stem requires additional in-stream flows. The watershed is one hosting multiple resources, a variety of users, and managed by an array of state and federal agencies. This study proposes a basis for securing in-stream flows for the Platte River. Candidate water supply mechanisms are suggested based on the way in which Casper, Wyoming secured water for its municipal needs. Canal lining is compared to a dam project, increasing reservoir storage, and purchasing water rights, with consideration also made for water pricing to reduce municipal use. Comparisons are based on economic efficiency, potential water conservation, and property rights criteria. Canal lining, coupled with demand management, is shown to conserve water best, given the set of efficiency and cost criteria for in-stream flow enhancement. The approach offers an opportunity to organize the water supply choice context in a transboundary watershed when quantitative information is limited.     

Mixed-Grass Prairie Canopy Structure and Spectral Reflectance Vary with Topographic Position

Managers of the nearly 0.5 million ha of public lands in North and South Dakota, USA rely heavily on manual measurements of canopy height in autumn to ensure conservation of grassland structure for wildlife and forage for livestock. However, more comprehensive assessment of vegetation structure could be achieved for mixed-grass prairie by integrating field survey, topographic position (summit, mid and toeslope) and spectral reflectance data. Thus, we examined the variation of mixed-grass prairie structural attributes (canopy leaf area, standing crop mass, canopy height, nitrogen, and water content) and spectral vegetation indices (VIs) with variation in topographic position at the Grand River National Grassland (GRNG), South Dakota. We conducted the study on a 36,000-ha herbaceous area within the GRNG, where randomly selected plots (1?km² in size) were geolocated and included summit, mid and toeslope positions. We tested for effects of topographic position on measured vegetation attributes and VIs calculated from Landsat TM and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data collected in July 2010. Leaf area, standing crop mass, canopy height, nitrogen, and water content were lower at summits than at toeslopes. The simple ratio of Landsat Band 7/Band 1 (SR71) was the VI most highly correlated with canopy standing crop and height at plot and landscape scales. Results suggest field and remote sensing-based grassland assessment techniques could more comprehensively target low structure areas at minimal expense by layering modeled imagery over a landscape stratified into topographic position groups.     

Tiger shark (Galeocerdo cuvier) abundance and growth in a subtropical embayment: evidence from 7 years of standardized fishing effort

The tiger shark (Galeocerdo cuvier Peron and Lesueur 1822) is a widely distributed predator with a broad diet and the potential to affect marine community structure, yet information on local patterns of abundance for this species is lacking. Tiger shark catch data were gathered over 7 years of tag and release research fishing (1991–2000, 2002–2004) in Shark Bay, Western Australia (25°45′S, 113°44′E). Sharks were caught using drumlines deployed in six permanent zones (~3 km² in area). Fishing effort was standardized across days and months, and catch rates on hooks were expressed as the number of sharks caught h⁻¹. A total of 449 individual tiger sharks was captured; 29 were recaptured. Tiger shark catch rate showed seasonal periodicity, being higher during the warm season (Sep–May) than during the cold season (Jun–Aug), and was marked by inter-annual variability. The most striking feature of the catch data was a consistent pattern of slow, continuous variation within each year from a peak during the height of the warm season (February) to a trough in the cold season (July). Annual growth rates of recaptured individuals were generally consistent with estimates from other regions, but exceeded those for populations elsewhere for sharks >275 cm fork length (FL), perhaps because mature sharks in the study area rely heavily on large prey. The data suggest that (1) the threat of predation faced by animals consumed by tiger sharks fluctuates dramatically within and between years, and (2) efforts to monitor large shark abundance should be extensive enough to detect inter-annual variation and sufficiently intensive to account for intra-annual trends.     

Acoustically detected year-round presence of right whales in an urbanized migration corridor

Species' conservation relies on understanding their seasonal habitats and migration routes. North Atlantic right whales (Eubalaena glacialis), listed as endangered under the U.S. Endangered Species Act, migrate from the southeastern U.S. coast to Cape Cod Bay, Massachusetts, a federally designated critical habitat, from February through May to feed. The whales then continue north across the Gulf of Maine to northern waters (e.g., Bay of Fundy). To enter Cape Cod Bay, right whales must traverse an area of dense shipping and fishing activity in Massachusetts Bay, where there are no mandatory regulations for the protection of right whales or management of their habitat. We used passive acoustic recordings of right whales collected in Massachusetts Bay from May 2007 through October 2010 to determine the annual spatial and temporal distribution of the whales and their calling activity. We detected right whales in the bay throughout the year, in contrast to results from visual surveys. Right whales were detected on at least 24% of days in each month, with the exception of June 2007, in which there were no detections. Averaged over all years, right whale calls were most abundant from February through May. During this period, calls were most frequent between 17:00 and 20:00 local time; no diel pattern was apparent in other months. The spatial distribution of the approximate locations of calling whales suggests they may use Massachusetts Bay as a conduit to Cape Cod Bay in the spring and as they move between the Gulf of Maine and waters to the south in September through December. Although it is unclear how dependent right whales are on the bay, the discovery of their widespread presence in Massachusetts Bay throughout the year suggests this region may need to be managed to reduce the probability of collisions with ships and entanglement in fishing gear.