Application of automated mass spectrometry deconvolution and identification software for pesticide analysis in surface waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Titration Curves: A Useful Instrument for Assessing the Buffer Systems of Acidic Mining Waters (10 pp)

Background, Aims and Scope The acidification of mine waters is generally caused by metal sulfide oxidation, related to mining activities. These waters are characterized by low pH and high acidity due to strong buffering systems. The standard acidity parameter, the Base Neutralization Capacity (BNC) is determined by endpoint titration, and reflects a cumulative parameter of both hydrogen ions and all buffering systems, but does not give information on the individual buffer systems. We demonstrate that a detailed interpretation of titration curves can provide information about the strength of the buffering systems. The buffering systems are of importance for environmental studies and treatment of acidic mining waters. Methods Titrations were carried out by means of an automatic titrator using acidic mining waters from Germany and Canada. The curves were interpreted, compared with each other, to endpoint titration results and to elemental concentrations contained therein. Results and Discussion The titration curves were highly reproducible, and contained information about the strength of the buffer systems present. Interpretations are given, and the classification and comparison of acidic mining waters, by the nature and strength of their buffering systems derived from titration curves are discussed. The BNC-values calculated from the curves were more precise than the ones determined by the standard endpoint titration method. Due to the complex buffer mechanisms in acidic mining waters, the calculation of major metal concentrations from the shape of the titration curve resulted in estimates, which should not be confused with precise elemental analysis results. Conclusion Titration curves provide an inexpensive, valuable and versatile tool, by which to obtain sophisticated information of the acidity in acidic water. The information about the strength of the present buffer systems can help to understand and document the complex nature of acidic mining water buffer systems. Finally, the interpretation of titration curves could help to improve treatment measurements and the ecological understanding of these acidic waters.     

Suitability of Crangonyx pseudogracilis (Crustacea: Amphipoda) as an Early Warning Indicator in the Multispecies Freshwater Biomonitor (9 pp)

Background Biological monitors are increasingly important in 'Biological Early Warning Systems' (BEWS) for monitoring water quality. This study examines the freshwater amphipod Crangonyx pseudogracilis as a potential new indicator species when used in the Multispecies Freshwater Biomonitor (MFB). The MFB is an online continuous biomonitor which uses impedance conversion to record behavioural responses of vertebrates and invertebrates. Methods Four experiments were undertaken to establish: (1) if the electrical field generated by the MFB affected the organisms' behaviour, (2) if defined behaviours and their response to a gradient of ammonium chloride could be detected by the MFB, (3) if there was variation in the behaviour of C. pseudogracilis over a diel cycle, and (4) if behaviour changed significantly in response to a pulse of ammonium chloride. Results and Discussion Results showed no significant effect of the MFB's current on behaviour of C. pseudogracilis. Four behaviours; swimming, walking, grooming and inactivity, were observed and identified in the MFB. In the MFB, each behaviour changed significantly in response to an increasing gradient of ammonium chloride exposure. The MFB also detected increases in nocturnal activity by C. pseudogracilis. The MFB also detected a significant increase in activity after a pulse of ammonium chloride. Conclusion The range of behaviours exhibited by Crangonyx pseudogracilis, together with its ease of culture, suggest future potential of this species as an indicator species for the Multispecies Freshwater Biomonitor. Recommendations and Perspective . Further testing is required over a range of toxicants and concentration gradients to establish threshold responses and the full compliment of behaviours that could be useful in online biomonitoring.     

Two-stage fuzzy-stochastic robust programming: a hybrid model for regional air quality management

In this study, a hybrid two-stage fuzzy-stochastic robust programming (TFSRP) model is developed and applied to the planning of an air-quality management system. As an extension of existing fuzzy-robust programming and two-stage stochastic programming methods, the TFSRP can explicitly address complexities and uncertainties of the study system without unrealistic simplifications. Uncertain parameters can be expressed as probability density and/or fuzzy membership functions, such that robustness of the optimization efforts can be enhanced. Moreover, economic penalties as corrective measures against any infeasibilities arising from the uncertainties are taken into account. This method can, thus, provide a linkage to predefined policies determined by authorities that have to be respected when a modeling effort is undertaken. In its solution algorithm, the fuzzy decision space can be delimited through specification of the uncertainties using dimensional enlargement of the original fuzzy constraints. The developed model is applied to a case study of regional air quality management. The results indicate that reasonable solutions have been obtained. The solutions can be used for further generating pollution-mitigation alternatives with minimized system costs and for providing a more solid support for sound environmental decisions.     

Influence of air-sea fluxes on chlorine isotopic composition of ocean water: implications for constancy in delta37Cl--a statistical inference

The behaviors of chlorine isotopes in relation to air-sea flux variables have been investigated through multivariate statistical analyses (MSA). The MSA technique provides an approach to reduce the data set and was applied to a set of 7 air-sea flux variables to supplement and describe the variation in chlorine isotopic compositions (delta37Cl) of ocean water. The variation in delta37Cl values of surface ocean water from 51 stations in 4 major world oceans--the Pacific, Atlantic, Indian and the Southern Ocean has been observed from -0.76 to +0.74 per thousand (av. 0.039+/-0.04 per thousand). The observed delta37Cl values show basic homogeneity and indicate that the air-sea fluxes act differently in different oceanic regions and help to maintain the balance between delta37Cl values of the world oceans. The study showed that it is possible to model the behavior of chlorine isotopes to the extent of 38-73% for different geographical regions. The models offered here are purely statistical in nature; however, the relationships uncovered by these models extend our understanding of the constancy in delta37Cl of ocean water in relation to air-sea flux variables.     

Ecotoxicological effect of grounded MV River Princess on the intertidal benthic organisms off Goa

The ecotoxicological effects of oil spill from the grounded vessel MV River Princess on the intertidal benthic organisms of Sinquerim-Candolim beach at Goa were investigated. An intertidal expanse of 1 km on either side of the grounded vessel was selected to evaluate the concentration of total petroleum hydrocarbon (TPH) in the sediment and its effects on the composition, abundance and diversity of micro-, meio- and macrobenthos. TPH in the intertidal sediment ranged from 7.8 to 89 microg g(-1) (mean 35.44+/-26.35 SD). Microbenthos comprised of microalgae, protozoans and juvenile forms of meiobenthos. Apart from juvenile nematodes, which were abundant, Coscinodiscus spp., Navicula spp., and Nitzschia spp. representing microalgae were also observed in microbenthic samples. Meiobenthos was represented by 13 taxa and their total density ranged between 92 and 1057 nos. 10 cm(-2). Maximum meiobenthic abundance of 1057 nos. 10 cm(-2) was observed at Sinquerim. Nematodes were the dominant meiobenthic taxa followed by turbellarians and harpacticoid copepods. The macrobenthos was numerically dominated by polychaetes, followed by crustaceans whereas bivalve molluscs were less represented. There was substantial increase in the petroleum concentration in the beach sediment compared to the previously reported values and highest TPH (89 microg g(-1) sediment) values were in the vicinity of the grounded vessel. The polychaete/amphipod ratio and cumulative and partial dominance abundance-biomass curves showed significant negative impact of TPH on macrofauna. The benthic community structure also showed measurable changes, as there was significant decrease (60%) in the number of species. Given that the microalgal counts were low in sediment, it is assumed that the intertidal meiofauna was possibly using oil-degrading bacteria as alternate food source. In conclusion, the results reported here suggest that the grounded ore carrier is not only detrimental to the beach community, that may take longer time for recovery, but also affects the beach morphology which may have long-term impact on local fishery.     

Assessment of ecotoxicological risks related to depositing dredged materials from canals in northern France on soil

The implementation of an ecological risk assessment framework is presented for dredged material deposits on soil close to a canal and groundwater, and tested with sediment samples from canals in northern France. This framework includes two steps: a simplified risk assessment based on contaminant concentrations and a detailed risk assessment based on toxicity bioassays and column leaching tests. The tested framework includes three related assumptions: (a) effects on plants (Lolium perenne L.), (b) effects on aquatic organisms (Escherichia coli, Pseudokirchneriella subcapitata, Ceriodaphnia dubia, and Xenopus laevis) and (c) effects on groundwater contamination. Several exposure conditions were tested using standardised bioassays. According to the specific dredged material tested, the three assumptions were more or less discriminatory, soil and groundwater pollution being the most sensitive. Several aspects of the assessment procedure must now be improved, in particular assessment endpoint design for risks to ecosystems (e.g., integration of pollutant bioaccumulation), bioassay protocols and column leaching test design.     

Limits of thermoluminescence dosimetry using quartz extracted from recent building materials in urban settlements

The luminescence of quartz extracted from recently fired building material is known to detect doses of few mGy and can be successfully employed in the case of large scale radiation exposures due to nuclear accidents or terrorist acts. One brick and two tiles (50-80 years range) collected from an urban settlement were used to test the realistic minimum detectable dose limits of retrospective luminescence dosimetry. Independent methods like alpha counting, beta dosimetry, gamma spectrometry and flame photometry were used for the annual dose assessment. Two approaches were employed for the evaluation of the total accrued dose: regenerative dose and additive dose. The former allows the assessment of doses due to anthropogenic sources of radiation as low as approximately 12 mGy by using 10-year-old samples, but it can be applied only in samples showing no sensitisation. The latter can be applied to any sample, however, the related uncertainty is higher and minimum detectable anthropogenic dose in young samples amounts to 20 mGy.     

The risk assessment-policy gap: an example from the UK contaminated land regime

Risk-based regulation assumes that risk assessment can evaluate risks against policy objectives. However, policy goals are often ambiguous and require risk assessors to interpret them for use in risk assessment. This risk assessment-policy gap stems partly from normative and imprecise policy language but is rooted more fundamentally in society's uncertain expectations for the environment. Until this uncertainty is resolved, the democratic and regulatory effectiveness of risk regulation will be undermined by ad hoc policy decisions abdicated to risk assessors.     

Radiological Dispersion Devices: are we prepared?

Already before the events of September 11th 2001 concern was raised about the spread of orphan sources and their potential use in Radiological Dispersion Devices by terrorist groups. Although most of the simulated scenarios foresee a rather limited direct health impact on the population, the affected region would suffer from the indirect consequences such as social disruption, cleanup requirements and economic costs. The nature of such a radiological attack would anyway be different compared to conventional radiological accidents, basically because it can happen anywhere at any time. Part of the response resides in a general preparedness scheme incorporating attacks with Radiological Dispersion Devices. Training of different potential intervention teams is essential. The response would consist of a prioritised list of actions adapted to the circumstances. As the psychosocial dimension of the crisis could be worse than the purely radiological one, an adapted communication strategy with the public aspect would be a key issue.