HPLC-MS/MS in der Rückstandsanalytik von Pflanzenschutzmitteln

Goal and Scope

Increasing demands from the regulatory authorities of plant protection products for residue analytical methods on the one hand and the need for cost reduction by shorter development times on the other hand have led to a significant displacement of conventional methods (e.g. HPLC-UV or GC-MS) by HPLC-MS/MS with atmospheric pressure ionization (API) in residue analysis since the mid of the 1990s. This development started in the pharmaceutical industries where HPLC-MS/MS had already been used for the quantitation of drugs and their metabolites in plasma since the late 1980s.

Methods

The reason for the high acceptability of HPLC-MS/MS with electrospray ionisation (ESI) or chemical ionization at atmosheric pressure (APCI) compared with alternative methods are shown with respect to analytical quality parameters, compliance with international registration guidelines and economic reasons.

Results and Conclusion

HPLC-MS/MS is being applied for solving ca. 75% of all analytical problems occuring in modern residue analytical laboratories. This technique offers convincing advantages for the determination of plant protection products and their metabolites in various matrices. These are a reduced number of or no clean-up steps after extraction of the samples, high throughput besides high ruggedness, low limits of detection and a large linear measuring range. In addition, several analytes of various chemical classes can be determined within one chromatographic run. Due to the high selectivity there is only little need for additional confirmatory methods. For enforcement purposes HPLC-MS/MS is accepted by the European authorities since 2002. However, due to high costs for instrumentation and specially skilled personnel only few enforcement laboratories have invested into this technology, so far.

Recommendation and Perspective

The importance of HPLC-MS/MS in residue analysis will further increase, as new ionization techniques will enable the analysis of more analytes and as the investment costs will decrease in the future. However, proven conventional methods will still survive in some cases. New concepts, such as parallel HPLC-MS/MS or on-line purification of extracts by column switching which are already widely used in the pharmaceutical industry could help to further increase the throughput. However, for a sound evaluation with respect to their applicability in residue analysis there is so far too little experience.     

Assessment of the Applicability of Capsid-Integrity Assays for Detecting Infectious Norovirus Inactivated by Heat or UV Irradiation

Food and Environmental Virology - Human noroviruses are the leading cause of viral gastroenteritis. In the absence of a practical culture technique for routine analysis of infectious noroviruses,...     

Size-assortative pairing across three developmental stages in the Zeus bug, Phoreticovelia disparata

The mechanisms underlying size-assortative pairing have received considerable attention. Typically, pairing is assumed to occur at, or just prior to, the adult phase of the life cycle. However, in many invertebrates, males commence associations with juvenile females who are more than a single moult away from sexual maturity. These species are ideal to explore the importance of reproductive and survival benefits as mechanisms driving size-assortative pairing. In the Zeus bug, Phoreticovelia disparata, adult males are found riding on juvenile (fourth and fifth instar) and adult females—a behaviour that is costly for females but has survival benefits for males. Using a combination of field collections and laboratory manipulations, we show that pairing is size-assortative both within and between female age classes and that riding males are smaller than non-riding males. In a series of mating trials, we revealed that males attempt to ride any female but that their riding success is dependent on female age. We also provide the first direct evidence of female resistance to male riding attempts in P. disparata. We propose that size-assortative pairing arises through adaptations that have evolved to minimise the potential costs of sexual conflict. We suggest that the selective pressure on males to maximise survival benefits is sufficiently high that it outweighs the reproductive benefits of discriminating against fourth instar females. Finally, given that female resistance is under direct selection in juvenile females, it is likely to be the main form of selective pressure for adult females.     

Zur Entwicklung einer Prüfstrategie auf sexual-endokrine Wirksamkeit einer chemischen Substanz bei Fischen

Ohne Zusammenfassung Hintergrundinformation Umweltbundesamt (2007). Abschlussbericht des Forschungsprojektes „Charakterisierung endokrin vermittelter Wirkungen in Fischen: Relevante Parameter für die Entwicklung einer neuen OECD-Testmethode und in der Anwendung in der gesetzlichen Umweltrisikobewertung“ im Auftrag des Umweltbundesamtes (F?rderkennzeichen 206 67 470). Online erh?ltlich unter     

Report: New guidelines for characterization of municipal solid waste: the Portuguese case

This report proposes a new set of guidelines for the characterization of municipal solid waste. It is based on an analysis of reference methodologies, used internationally, and a case study of Valorsul (a company that handles recovery and treatment of solid waste in the North Lisbon Metropolitan Area). In particular, the suggested guidelines present a new definition of the waste to be analysed, change the sampling unit and establish statistical standards for the results obtained. In these new guidelines, the sampling level is the waste collection vehicle and contamination and moisture are taken into consideration. Finally, focus is on the quality of the resulting data, which is essential for comparability of data between countries. These new guidelines may also be applicable outside Portugal because the methodology includes, besides municipal mixed waste, separately collected fractions of municipal waste. They are a response to the need for information concerning Portugal (e.g. Eurostat or OECD inquiries) and follow European Union municipal solid waste management policies (e.g. packaging waste recovery and recycling targets and the reduction of biodegradable waste going to landfill).     

Clean development mechanism: an incentive for waste management projects?

The Clean Development Mechanism (CDM) was introduced by the Kyoto Protocol to provide a financial incentive to establish project activities in developing countries for reducing greenhouse gas emissions while also fostering sustainable development. This article shows that waste management project activities play an important role in achieving the aims of the CDM. It describes how these activities have to prove additionality, how the emission reductions must be calculated and monitored in order to be eligible and in order to lead to Certified Emission Reductions (CERs). The article further provides an analysis about the various challenges that are involved in applying the CDM scheme to waste management project activities, which require a new specific set of technical skills and regulatory standards.     

Testing of a GIS model ofEucalyptus Iargiflorens health on a semiarid,saline floodplain

Irrigated agriculture has resulted in substantial changes in water flows to the lower reaches of the River Murray. These changes have led to large-scale occurrences of dieback inEucalyptus largiflorens (black box) woodlands as well as increased inputs of salt to the river. Management options to address problems of this scale call for the use of spatial data sets via geographic information systems (GIS). A GIS exists for one floodplain of the River Murray at Chowilla, and a simple model predicted six health classes ofEucalyptus largiflorens based on groundwater salinity, flooding frequency, and groundwater depth.To determine the usefulness of the model for vegetation management, the quality of both the model and the GIS data sets were tested. Success of the testing procedure was judged by the degree of spatial matching between the model's predictions of health and that assessed from aerial photographs and by field truthing. Analyses at 80 sites showed that tree health was significantly greater where groundwater salinity was less than 40 dS/m or flooding occurred more frequently than 1 in 10 years or depth to groundwater exceeded 4 m. Testing of the GIS data sets found that vegetation was misclassified at 15% of sites. Association was shown between GIS-predicted values and field-truthed values of groundwater salinity but not groundwater depth. The GIS model of health is a useful starting point for future vegetation management and can be further improved by increasing the quality of the data coverages and further refining of the model to optimize parameters and thresholds.     

A national critical loads framework for atmospheric deposition effects assessment: II. Defining assessment end points,indicators, and functional subregions

The United States Environmental Protection Agency, with support from the US Department of Energy and the National Oceanographic and Atmospheric Administration, has been evaluating the feasibility of an effects-based (critical loads) approach to atmospheric pollutant regulation and abatement. The rationale used to develop three of the six steps in a flexible assessment framework (Strickland and others, 1992) is presented along with a discussion of a variety of implementation approaches and their ramifications. The rationale proposes that it is necessary to provide an explicit statement of the condition of the resource that is considered valuable (assessment end point) because: (1) individual ecosystem components may be more or less sensitive to deposition, (2) it is necessary to select indicators of ecosystem condition that can be objectively measured and that reflect changes in the quality of the assessment end point, and (3) acceptable status (i.e., value of indicator and quality of assessment end point at critical load) must be defined. The rationale also stresses the importance of defining the assessment regions and subregions to improve the analysis and understanding of the indicator response to deposition. Subregional definition can be based on a variety of criteria, including informed judgment or quantitative procedures. It also depends on the geographic scale at which exposure and effects models are accurate and on data availability, resolution, and quality. The research described in this article has been funded by the US Environmental Protection Agency. This document has been prepared at the EPA Environmental Research Laboratory in Corvallis, Oregon, through contract #68-C8-0006 with ManTech Environmental Technology, Inc., and Interagency Agreement #1824-B014-A7 with the US Department of Energy and at Oak Ridge National Laboratory managed by Martin Marietta Energy Systems, Inc., under Contract DE-AC05-84OR21400 with the US Department of Energy. Environmental Sciences Division Publication No. 3903. It has been subjected to the agency’s peer and administrative review and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use.     

FRESH GROUND WATER STORED IN AQUIFERS UNDER THE CONTINENTAL SHELF: IMPLICATIONS FROM A DEEP TEST,NANTUCKET ISLAND,MASSACHUSETTS1

ABSTRACT: A deep water-resource and stratigraphic test well near the center of Nantucket Island, about 40 miles (64 km) off the New England Coast, has encountered freshwater at greater depth than predicted by the Ghyben-Herzberg principle. An uppermost lens of fresh-water, which occupies relatively permeable glacial-outwash sand and gravel to a depth of 520 ft. (158 m), is probably in hydrodynamic equilibrium with the present level of the sea and the height of the water table. However, two zones of freshwater between 730-820 ft. (222-250 m) and 900-930 ft. (274-283 m) are anomalously deep. A third zone extending from 1150-1500 ft. (350-457 m) contains slightly salty ground water (2 to 3 parts per thousand dissolved solids). Several explanations are possible, but the most likely is that large areas of the Continental Shelf were exposed to recharge by precipitation during long periods of low sea level in Pleistocene time. After the last retreat of glacial ice, seawater rapidly drowned the shelf around Nantucket Island. Since then, about 8000 years ago, the deep freshwater zones which underlie dense clay layers have not had time to adjust to a new equilibrium. Under similar circumstances freshwater may remain trapped under extensive areas of the Continental Shelf wherever clay confining beds have not permitted saltwater to intrude rapidly to new positions of hydrodynamic equilibrium. The implications are far reaching because all continental shelfs were exposed to similar hydrologic influences during Pleistocene time.