Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Health and environmental costs of pesticide use in vegetable farming in Nepal

There is a growing concern of pesticide risks to human health, natural environment and ecosystems. Many previous economic valuations have accounted health aspects or environmental components, but rarely combined; thus, overall risk assessment is partially distorted. The study, conducted close to the capital of Nepal, addressed the health effects of pesticides on small-scale farmers and evaluated the monetary risks of pesticide use on human health and environmental resources. We also aim to establish the relationships among valuation methods. The paper adopts cost of illness, defensive expenditure and contingent valuation willingness to pay approach. The study concluded that the methods used for valuing pesticide risks to human and environmental health are theoretically consistent. The exposed individuals are likely to bear significant economic costs of exposures depending on geographical location, pesticide use magnitudes and frequency. Individuals are willing to pay between 53 and 79% more than the existing pesticide price to protect their health and environment. The integrated pest management training is less likely to reduce health costs of pesticide exposure, although it leads to higher investment in safety measures.     

Bioluminescence in the high Arctic during the polar night

This study examines the composition and activity of the planktonic community during the polar night in the high Arctic Kongsfjord, Svalbard. Our results are the first published evidence of bioluminescence among zooplankton during the Arctic polar night. The observations were collected by a bathyphotometer detecting bioluminescence, integrated into an autonomous underwater vehicle, to determine the concentration and intensity of bioluminescent flashes as a function of time of day and depth. To further understand community dynamics and composition, plankton nets were used to collect organisms passing through the bathyphotometer along with traditional vertical net tows. Additionally, using a moored bathyphotometer closed to the sampling site, the bioluminescence potential itself was shown not to have a diurnal or circadian rhythm. Rather, our results provide evidence for a diel vertical migration of bioluminescent zooplankton that does not correspond to any externally detectable changes in illumination.     

Boldness and body size of male Spanish terrapins affect their responses to chemical cues of familiar and unfamiliar males

Recognition and avoidance of conspecifics based on chemical cues could reduce the risk of aggressive interactions between males. Success in agonistics encounters with unfamiliar males should be lower than with previously known familiar males. Then, males should avoid the chemicals from unfamiliar males with respect to those from familiar males. However, boldness and size could affect the outcome of encounters between males and, consequently, the response to chemical cues of conspecific males. We compared the time spent by male turtles Mauremys leprosa in water pools with chemical stimuli from unfamiliar or familiar males or with their own chemical stimuli. We also performed a behavioral test to estimate boldness of turtles in an antipredatory situation. Turtles avoided the chemicals from unfamiliar males respect to familiar ones and their own odors, but their responses depended on boldness and size of the tested turtle. Bold turtles avoided water with chemicals of unfamiliar males, but not with chemicals of familiar males, whereas shy turtles avoided chemicals of both familiar and unfamiliar males. On the other hand, large males avoided the odor from unfamiliar males, but small males did not avoid water with the odor from other males. Results suggest that male M. leprosa can detect chemicals released to water from conspecific males and discriminate between familiar and unfamiliar males. However, responses to these chemicals depended on boldness and body size of the responding turtle because these factors may affect intrasexual competition.     

Ultraviolet absorption in transparent zooplankton and its implications for depth distribution and visual predation

The use of transparency as camouflage in the epipelagic realm is complicated by the presence of ultraviolet radiation, because the presence of UV-protective pigments decreases UV transparency and may reveal transparent zooplankton to predators and prey with UV vision. During July 1999, September 1999, and June 2000, transparency measurements (from 280 to 500 nm) were made on living specimens of 15 epipelagic (collection depth: 0–20 m, average: 11 ± 1 m) and 19 mesopelagic (collection depth: 150–790 m, average: 370 ± 40 m) species of transparent zooplankton from Oceanographer Canyon and Wilkinson Basin in the Northwest Atlantic Ocean. In addition, measurements of downwelling irradiance (from 330 to 500 nm) versus depth were made. The tissues from epipelagic zooplankton had lower UV transparency than those from mesopelagic zooplankton, while the average visible transparency (at 480 nm) of the two groups was not significantly different. Percent transparency was positively correlated with wavelength over most of the measured range, with a rapid decrease below a certain cutoff wavelength. In mesopelagic tissues, the cutoff wavelength was generally 300 nm. In epipelagic tissues, the cutoff wavelength was between 300 and 400 nm. Twelve out of 19 epipelagic tissues had transparencies at 320 nm that were half or less than their 480 nm transparency values, versus only 4 out of 21 mesopelagic tissues. The effects of UV absorption on UV visibility and minimum attainable depth were modeled using contrast theory and the physics of light attenuation. Because UV absorption was generally significantly greater in the UVB than in the UVA spectrum (where UV vision occurs), and because the highest UV absorption was often found in less transparent individuals, its modeled effects on visibility were slight compared to its effects on minimum attainable depth. Received: 14 April 2000 / Accepted: 16 November 2000     

Metabolites of the phenylurea herbicides chlorotoluron, diuron, isoproturon and linuron produced by the soil fungus Mortierella sp.

Phenylurea herbicides are used worldwide, and often pollute surface- and groundwater in concentrations exceeding the limit value for drinking water (0.1 μg l⁻¹). Bacteria degrade phenylurea herbicides by successive N-dealkylation to substituted aniline products. Little is known about the corresponding fungal pathways, however. We here report degradation of chlorotoluron, diuron, isoproturon and linuron by the soil fungus Mortierella sp. Gr4. Degradation was fastest with linuron and resulted in successively dealkylated metabolites and 3,4-dichloroaniline. A major new metabolite was detected that has not yet been fully identified. Thin layer chromatography and nuclear magnetic resonance spectroscopy indicate that it is a non-aromatic diol. Degradation of isoproturon, chlorotoluron and diuron involved successive N-demethylation and, in the case of isoproturon and chlorotoluron, additional hydroxylation. A new hydroxylated isoproturon metabolite was detected. The study thus shows that the fungal pathways differ from the bacterial pathways and yield new metabolites of possible environmental concern.     

Continuing Issues in the Limitations of Pesticide Use in Developing Countries

The rationale for pesticide use in agriculture is that costs associated with pesticide pollution are to be justified by its benefits, but this is not so obvious. Valuing the benefits by simple economic analysis has increased pesticide use in agriculture and consequently produced pesticide-induced “public ills.” This paper attempts to explore the research gaps of the economic and social consequences of pesticide use in developing countries, particularly with an example of Nepal. We argue that although the negative sides of agricultural development, for example- soil, water, and air pollution; pest resistance and resurgence; bioaccumulation, bio-magnification; and loss of biodiversity and ecosystem resilience caused by the use of pesticides in agriculture, are “developmental problems” and are “unintentional,” the magnitude may be increased by undervaluing the problems in the analysis of its economic returns. Despite continuous effort for holistic system analyses for studying complex phenomena like pesticides impacts, the development within the academic science has proceeded in the opposite direction that might have accelerated marginalization of the third world subsistence agricultural communities. We hypothesize that, if these adversities are realized and accounted for, the benefits from the current use of pesticides could be outweighed by the costs of pollution and ill human health. This paper also illustrates different pathways and mechanisms for marginalization. In view of potential and overall negative impacts of pesticide use, we recommend alternative ways of controlling pests such as community integrated pest management (IPM) along with education and training activities. Such measures are likely to reduce the health and environmental costs of pesticide pollution, and also enhance the capabilities of third world agricultural communities in terms of knowledge, decision making, innovation, and policy change.     

Monitoring, modelling and environmental exposure assessment of industrial chemicals in the aquatic environment

Monitoring and laboratory data play integral roles alongside fate and exposure models in comprehensive risk assessments. The principle in the European Union Technical Guidance Documents for risk assessment is that measured data may take precedence over model results but only after they are judged to be of adequate reliability and to be representative of the particular environmental compartments to which they are applied. In practice, laboratory and field data are used to provide parameters for the models, while monitoring data are used to validate the models' predictions. Thus, comprehensive risk assessments require the integration of laboratory and monitoring data with the model predictions. However, this interplay is often overlooked. Discrepancies between the results of models and monitoring should be investigated in terms of the representativeness of both. Certainly, in the context of the EU risk assessment of existing chemicals, the specific requirements for monitoring data have not been adequately addressed. The resources required for environmental monitoring, both in terms of manpower and equipment, can be very significant. The design of monitoring programmes to optimise the use of resources and the use of models as a cost-effective alternative are increasing in importance. Generic considerations and criteria for the design of new monitoring programmes to generate representative quality data for the aquatic compartment are outlined and the criteria for the use of existing data are discussed. In particular, there is a need to improve the accessibility to data sets, to standardise the data sets, to promote communication and harmonisation of programmes and to incorporate the flexibility to change monitoring protocols to amend the chemicals under investigation in line with changing needs and priorities.