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.     

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.     

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     

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.     

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.     

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.     

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.     

Limited microbial degradation of pyrene metabolites from the estuarine polychaete Nereis diversicolor

We compared microbial mineralization of [4,5,9,10-14C]pyrene and its eukaryotic [4,5,9,10-14C]pyrene metabolites in estuarine sediments. Metabolites were obtained by exposing the estuarine deposit-feeding polychaete Nereis diversicolor to sediment-associated 14C-pyrene, followed by homogenization of the worms and extraction of the pyrene-metabolites. In sediment from a pristine Danish Fjord only 2.6% of the added metabolite-label and 1.7% of the pyrene-label were mineralized to 14CO2 during 175 days incubation. Pre-exposure of the pristine sediment to unlabelled pyrene for 60 days increased the mineralization potential for 14C-pyrene substantially, as 81.2% was mineralized to 14CO2 during 95 days incubation, whereas 14C-pyrene metabolite label was unaffected by pre-exposure to pyrene. In comparison, naturally aged bunker-oil contaminated sediment did not show elevated potentials for mineralization of neither 14C-pyrene nor 14C-metabolites. Six bacterial strains of known pyrene degraders were tested for growth on crystalline 1-hydroxypyrene. 1-Hydroxypyrene is the only intermediate eucaryotic metabolite of pyrene. The results indicate that 1-hydroxypyrene was not utilized as a sole source of carbon and energy by any of them. In addition, respiration was depressed in all six strains when exposed to crystalline 1-Hydroxypyrene, demonstrating an acute toxic effect of 1-hydroxypyrene. The results presented here suggest that microbial degradation of pyrene is not enhanced by release of aqueous and polar metabolites by marine invertebrates.     

Predicting biodiversity change: outside the climate envelope, beyond the species-area curve

Efforts to anticipate threats to biodiversity take the form of species richness predictions (SRPs) based on simple correlations with current climate and habitat area. We review the major approaches that have been used for SRP, species-area curves and climate envelopes, and suggest that alternative research efforts may provide more understanding and guidance for management. Extinction prediction suffers from a number of limitations related to data and the novelty of future environments. We suggest additional attention to (1) identification of variables related to biodiversity that are diagnostic and potentially more predictable than extinction, (2) constraints on species dispersal and reproduction that will determine population persistence and range shifts, including limited sources or potential immigrants for many regions, and (3) changes in biotic interactions and phenology. We suggest combinations of observational and experimental approaches within a framework available for ingesting heterogeneous data sources. Together, these recommendations amount to a shift in emphasis from prediction of extinction numbers to identification of vulnerabilities and leading indicators of change, as well as suggestions for surveillance tools needed to evaluate important variables and the experiments likely to provide most insight.     

Morphologic development, relative sea level rise and sustainable management of water and sediment in the Ebre Delta, Spain

The Ebre (Ebro) Delta is one of the most important wetland areas in the western Mediterranean. Ca. 40 % of the delta plain is less than 0.5 m above mean sea level and part of the southern margin of the delta is at mean sea level in an area protected by dikes. Both mean rates of secular subsidence in the Ebre Delta and eustatic sea level rise are ca. 1 – 2 mm/yr. Thus, the present annual relative sea level rise (RSLR) rate in the Ebre Delta may be at least 3 mm/yr. Measured accretion rates in the delta range from 4 mm/yr in the wetlands surrounding the river mouth to <0.1 mm/yr in impounded salt marshes and rice fields. The annual sediment deficit in the delta plain to offset RSLR is close to 1 million m³/yr. Accretion rates in the rice fields prior to the construction of large dams in the Ebre watershed were higher than RSLR rates, from 3 – 15 mm/yr. At present, >99 % of the riverine sediments are retained in the reservoirs and rice fields are losing ca. 0.2 mm/yr. Future management plans should take RSLR into account and include control of freshwater and sediment flows from the river in order to offset negative effects from waterlogging and salt intrusion, and maintain land elevation. This will include the partial removal of sediments trapped behind the Ribarroja and Mequinença dams. Stocks and inputs of sediments in the corresponding reservoirs are large enough for land elevation of ca. 50 cm in the whole delta plain. Advantages of this solution include (1) new sediments to the delta to offset subsidence (via rice fields) and coastal retreat, (2) enhanced functioning of the delta (productivity and nutrient processing), (3) avoidance of accumulation of sediments in the reservoirs. Hence, it is important to manage river discharges at the dams from an integrated viewpoint, whereas currently only hydropower and agricultural requirements are considered. It is also crucial to maintain periods of high discharge, to have enough river energy to transport as much sediments as possible.