Determination of atrazine in surface waters by combination of POCIS passive sampling and ELISA detection

Polar organic compound integrative samplers (POCIS) in combination with instrumental techniques such as LC-MS-MS were previously used to monitor environmental pollutants but the performance of alternative immunochemical methods such as ELISA (enzyme-linked immunosorbent assay) has been explored less. In the present study, POCIS technology was applied to surface water sampling in the Czech Republic, and ELISA was used as a detection technique for the herbicide atrazine. In the first study, 28 samples from streams around small municipal waste water treatment plants (WWTPs) were collected using two different devices (POCISpest and POCISpharm) over the course of 21 days. Elevated atrazine concentrations (up to 25 ng per POCIS) were found in samples down-stream of WWTPs. This observation was also confirmed in another two year study (4 sampling periods) investigating 7 river sites around a major city of Brno as well as the inlet and outlet of the city's WWTP. High atrazine levels were systematically determined at the outlet from the WWTPs (120-605 ng per POCIS). A decreasing trend in the atrazine concentrations in rivers around the city of Brno has been observed, with the highest levels observed within the first sampling period in spring 2007 (100-600 ng per POCIS, with an extreme value of 2760 ng per POCIS). Results of the atrazine ELISA were closely correlated with LC-MS/MS, which confirmed good applicability of ELISA as a cost-effective screening tool.     

Infrared differential absorption Lidar (DIAL) measurements of hydrocarbon emissions

We report the application of an infrared (IR) differential absorption Lidar (DIAL) system (also capable of ultra violet measurements) built at the National Physical Laboratory (NPL), UK, to field measurements of total site emissions (controlled and fugitive) from petrochemical and landfill installations. The validation of the IR-DIAL was carried out via a series of controlled field experiments including comparison to GC analysis and tests against controlled methane releases from a test stack, all detailing agreements on the order of ±20%. In volatile organic compound (VOC) measurements at a UK petrochemical site it was found that the American Petroleum Institute's methodology of the time for calculating the emitted flux underestimated by a factor of 2.4. Also, in a similar field trial it was found that scaling traditional point measurements at easily accessible flanges and valves to represent all flanges and valves on a site led to an underestimation by a factor of 6. In addition to petrochemical examples we also report field measurements from a landfill site to demonstrate the advantageous of the DIAL technique for monitoring area emission sources. In this case study it was found that active (still being filled) cells resulted in significantly greater VOC emission rates (30 kg h(-1)) than closed (≤ 10 kg h(-1)).     

House sparrows selectively eject parasitic conspecific eggs and incur very low rejection costs

Most host species of obligate interspecific brood parasites are under strong selection because such parasitism, e.g., that involving evictor nestmates, is highly costly. Egg rejection is one of the most efficient host defences against avian brood parasites. Many hosts have thus evolved egg-recognition ability and rejection behaviour. However, this defensive mechanism has not evolved in most species where only intraspecific brood parasitism occurs, probably because (1) the eggs of conspecific females are very similar in appearance, making egg rejection less likely to emerge, and (2) such parasitism is frequently less costly than interspecific parasitism. Using a captive population of house sparrows (Passer domesticus) with a low breeding density, we here provide new evidence showing that this species actually has a fine capacity to discriminate conspecific eggs and to eject them (44.2% of foreign eggs ejected) while incurring very low rejection costs (4.2% of own eggs ejected). This result contradicts those previously found in high-density house sparrow populations in which very high rejection costs and very high clutch desertion rates were reported, probably as a consequence of intraspecific competition and infanticide provoked by the high breeding density. The house sparrow has only rarely been reported as the host of an interspecific brood parasite, which implies that it is a newly described example of an altricial species in which egg ejection has evolved and is maintained in response to intraspecific brood parasitism.     

Biocatalytic dechlorination of hexachlorocyclohexane by immobilized bio-Pd in a pilot scale fluidized bed reactor

Lindane (??-hexachlorocyclohexane, ??-HCH) is a recalcitrant and toxic organochlorine insecticide. Due to its non-selective production process and widespread use, HCH isomers and their degradation products have been detected frequently in soils and groundwater. An innovative technology using microbial produced Pd(0) nanoparticles, i.e. bio-Pd, was developed to treat groundwater containing a mixture of HCHs and chlorobenzenes. In a first step, the groundwater was de-ironized and most of the chlorobenzenes were removed in a biological trickling filter. The ??g?L^?1 levels of HCHs and chlorobenzenes were removed in a second step by the bio-Pd-based technology. Therefore, a 200-L pilot scale reactor was developed with 100?mg?L^?1 bio-Pd encapsulated in alginate beads. Hydrogen gas was bubbled at the bottom of the reactor and served to charge the bio-Pd catalyst. The reactor influent contained 5.2???g?L^?1 HCHs and 51.1???g?L^?1 chlorobenzenes. During a test period of 10?days, 29% of the HCH isomers and 63% of the chlorobenzenes were removed applying a nominal hydraulic residence time of 4?h. These removal percentages could be increased to 75 and 68% by doubling the nominal hydraulic residence time to 8?h. This study demonstrated that biologically produced nanoparticles of Pd can be applied for the large-scale remediation of groundwater contaminated with HCHs.     

Voltammetric determination of the herbicide Bifenox in drinking and river water using a silver solid amalgam electrode

A new method for the determination of submicromolar and nanomolar concentrations of herbicide Bifenox using differential pulse voltammetry at a mercury meniscus modified silver solid amalgam electrode is described. This new type of working electrode is non-toxic, environmentally friendly, and compatible with principles of green analytical chemistry, and its surface can be easily electrochemically renewed in the case of passivation. The newly developed direct differential pulse voltammetric determination of Bifenox gives limit of determination 6.7·10^?7 and 6.9·10^?7?M in drinking and river water, respectively. Both the selectivity and the sensitivity can be further increased by preliminary separation and preconcentration using solid phase extraction. This combination enables to reach limit of determination 0.9?×?10^?9 and 1.5?×?10^?9?M for drinking and river water, respectively. Because of lower running and investment costs, this electroanalytical method can be used for large scale monitoring of possible water contamination with tested herbicide.     

Influence of season,ontogeny and tide on the diet of the temperate marine herbivorous fish Odax pullus (Odacidae)

The diet of the temperate marine herbivorous fish Odax pullus (Pisces: Odacidae) was examined using gut-content analysis followed by principal-component analysis and analysis of variance. Fish were collected near Leigh, on the northeast coast of New Zealand, from February 1983 to September 1984. The data were categorised by size of fish, season, and state of tide. A major ontogenetic shift in diet was observed. Juveniles fed on animal material (crustaceans and gastropods), epiphytic rhodophytes, and some phaeophyte material. Adults fed almost exclusively on two phaeophyte taxa, the laminarian Ecklonia radiata and the fucoid Carpophyllum spp. Dietary selection was evident at the level of particular plant components; the diet of larger fish in spring samples was dominated by fucoid reproductive receptacles. There was no direct evidence of a tidal influence on diet composition of O. pullus, although the relative proportions of E. radiata and Carpophyllum spp. ingested by adult fish appeared to vary with tidal state. The volume of gut contents varied seasonally for all size classes, although the timing of peak annual food intake varied among size classes. Tidal state did not influence the volume of the gut contents. The ontogenetic and seasonal trends evident in the diet of O. pullus appeared to be related to a number of factors including relative gut length, gonad development, ontogenetic changes in feeding anatomy and seasonal changes in algal composition.     

Identification, synthesis and activity of sex pheromone gland components of the autumn gum moth (Lepidoptera: Geometridae), a defoliator of Eucalyptus

Summary. The autumn gum moth, Mnesampela privata (Guenée) (Lepidoptera: Geometridae), is native to Australia and can be a pest of plantation eucalypts. Field-collected and laboratory-reared female autumn gum moths were dissected to remove glands likely to contain components of the sex pheromone. Using gas chromatography (GC) and combined gas chromatography–mass spectrometry (GC-MS), three compounds were identified from female extracts, namely (3Z,6 Z,9 Z)-3,6,9-nonadecatriene, 1-hexadecanol and 1-octadecanol (confirmed by comparison with synthetic samples). Nonadecatriene elicited an antennal response in male autumn gum moth during gas chromatographic analyses combined with electroantennographic detection (GC-EAD). In electroantennogram (EAG) recording male M. privata antennae responded to the nonadecatriene. Nonadecatriene was synthesised via Kolbe electrolysis, starting with (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid (linolenic acid) and propanoic acid or via an alternative four-step method also starting from linolenic acid. In field trials (3Z,6Z,9Z)-3,6,9-nonadecatriene proved attractive to male moths. Thus, we conclude that (3Z,6Z,9Z)-3,6,9- nonadecatriene is a sex pheromone component of autumn gum moth. This component has been identified in extracts from other geometrids in the same subfamily, Ennominae. However, to our knowledge this is the first example where (3Z,6Z,9Z)-3,6,9-nonadecatriene has been found in females and also proved attractive to male moths when presented on its own. Our results are discussed in relation to other geometrid pheromones.     

TNT in Komposten und Flüssigkultur

The formation of aromatic amines was investigated using a summarized test (NEDA-test) during the composting of 2,4,6-trinitrotoluene (TNT) contaminated soil. In this test, the aromatic amines were diazolated and then coupled to N-1-Naphthyl-ethylenediamine-dihydrochloride (NEDA) to yield an azo dye which can be monitored photometrically. The test was calibrated for known TNT-metabolites with an active amine-group. Liquid samples from composting- and liquid-culture-experiments were analyzed by HPLC for these known metabolites. Moreover, the samples were monitored by the NEDA-test and the expected extinction of the TNT-metabolites found with amine function were extrapolated with the help of calibration curves. It was shown that substantial differences are obvious between the monitored and extrapolated values. After separation into polar and non-polar aromatic amines, it became clear that these differences are made by the polar aromatic amines. Polar aromatic amines, which are not detectable by presently available analytical tests, were generated during the composting of TNT-contaminated soils. Contaminated stagnant water, which was generated during anaerobization of a compost prephase, was treated aerobically for 70 days in a biofermenter. During this treatment TNT and its known metabolites were eliminated almost entirely. Simultaneously, the toxicity in the Lumis Tox-test decreased drastically. In striking contrast, the sum of aromatic amines decreased only to a minor extent. Moreover, the percentage of polar compounds from total amount of aromatic amines increased drastically from 48% to more than 95%. At present, the chemical identification of these polar compounds is still missing and is the object for further research.     

A simulation model for the effects of burning on the phosphorus and nitrogen cycle of a heathland ecosystem

In this paper, a simulation model is presented for nutrient cycling in heathland ecosystems. The results of simulations are compared with field data of phosphorus and nitrogen accumulation in different compartments of the system in the years after burning, given in the literature on this subject (Chapman, 1967; 1970). It is shown that for the cycling of P the system returns slowly to equilibrium after an initial disturbance. The time span of about 30 years that is required to reach equilibrium is in agreement with the field data. However, P accumulation in living above-ground biomass and litter is overestimated by the model in the first years after burning. Nitrogen accumulation in biomass and litter is systematically underestimated by the model.The results are discussed with reference to the processes in nutrient cycling that are insufficiently understood, and with reference to the management of heathlands.