Microbial degradation of the benzonitrile herbicides dichlobenil, bromoxynil and ioxynil in soil and subsurface environments--insights into degradation pathways, persistent metabolites and involved degrader organisms

The benzonitriles dichlobenil, bromoxynil and ioxynil are important broad-spectrum or selective herbicides used in agriculture, orchards and public areas worldwide. The dichlobenil metabolite 2,6-dichlorobenzamide is the most frequently encountered groundwater contaminant in Denmark, which suggests that the environmental fate of these three structurally related benzonitrile herbicides should be addressed in detail. This review summarises the current knowledge on microbial degradation of dichlobenil, bromoxynil and ioxynil with particular focus on common features of degradation rates and pathways, accumulation of persistent metabolites and diversity of the involved degrader organisms.     

A possible prenatal evaluation of renal function by amino acid analysis on fetal urine

Intrauterine treatment of 4 fetuses with urethral obstruction was attempted in the third trimester of pregnancy. The fetuses displayed varying sonographic findings including pyelectasis, caliectasis, hydroureter, bladder dilatation, ascites, hydrops, missing kidneys and oligohydramnios. Ultrasonically guided aspiration from the dilated structures was carried out to relieve pressure on the kidney parenchyme and to collect fluid samples for diagnostic purposes. Amino acid concentrations in the fetal urine showed a pattern similar to plasma in 2 fetuses, a pattern almost like urine in 1 fetus and an intermediate pattern in the 4th fetus. Only the fetus with normal amino acid concentrations in the urine survived: the other 3 died in uremia shortly after birth. In 3 cases cells from the aspirated urine were cultured and used for chromosome analysis. The cell cultures grew fast and karyotyping was possible within 1 week. In 2 fetuses an intrauterine catheter was inserted to drain the kidney permanently into the amniotic cavity. In the first case the catheter was displaced to the fetal abdomen after some days of successful drainage. In the second case the catheter tore the placenta, and the child had to be delivered immediately.     

A chemical view of the most ancient metazoa--biomarker chemotaxonomy of hexactinellid sponges

Hexactinellid sponges are often considered to be the most ancient metazoans. Lipid biomarkers from 23 species were studied for information on their phylogenetic properties, particularly their disputed relation to the two other sponge classes (Demospongiae, Calcarea). The most prominent lipid compounds in the Hexactinellida comprise C28 to C32 polyenoic fatty acids. Their structures parallel the unique patterns found in demosponge membrane fatty acids ('demospongic acids') and strongly support a close phylogenetic association of the Demospongiae and the Hexactinellida. Both taxa also show unusual mid-chain methylated fatty acids (C15-C25) and irregular C25- and C40-isoprenoid hydrocarbons, tracers for specific eubacteria and Archaea, respectively. These biomarkers indicate a similar, highly conservative symbiont community, although some shift in the abundance of the associated microbiota was observed. The lack of these features in calcareous sponges further contradicts the still common view that Calcarea and Demospongiae are more closely related to each other than either is to the Hexactinellida.     

Recovery from acidification in Swedish forest streams

Sulphur deposition in Sweden has decreased to less than half of the levels recorded in 1970 and now signs of recovery from acidification of surface waters are beginning to appear. We investigated time trends of water chemistry between 1985 and 1998 in 13 streams draining small forested catchments with generally shallow acid sensitive soils. At nine of the catchments, bulk deposition was monitored as well. Sulphate concentrations decreased in both stream water and deposition, although with somewhat smaller trends in stream water compared with deposition. The magnitude of the trends in sulphate increased from north to south, following a gradient of increasing industrial influence. Five sites in the southern half of the country showed weak signs of recovery from acidification in terms of increasing concentrations of acid neutralising capacity and decreasing concentrations of hydrogen ions, corresponding to annual increases of 0.01 pH units. Changes in stream discharge and concentrations of marine salts and organic acids could not explain the observed decrease in acidity and the results were interpreted as recovery from anthropogenic acidification. For the northern half of Sweden, any changes in water chemistry could be attributed to natural variation in climate and marine influence, and the effect of anthropogenic acidification was negligible.     

Biodegradation of aromatic compounds by white rot and ectomycorrhizal fungal species and the accumulation of chlorinated benzoic acid in ectomycorrhizal pine seedlings

The capability of different white rot (WR, Heterobasidion annosum, Phanerochaete chrysosporium, Trametes versicolor) and ectomycorrhizal (ECM, Paxillus involutus, Suillus bovinus) fungal species to degrade different aromatic compounds and the absorption of 3-chlorobenzoic acid (3-CBA) by ECM pine seedlings was examined. The effect of aromatic compounds on the fungal biomass development varied considerably and depended on (a) the compound, (b) the external concentration, and (c) the fungal species. The highest effect on the fungal biomass development was observed for 3-CBA. Generally the tolerance of WR fungi against aromatic compounds was higher than that of the biotrophic fungal species. The capability of different fungi to degrade aromatic substances varied between the species but not generally between biotrophic and saprotrophic fungi. The highest degradation capability for aromatic compounds was detected for T. versicolor and H. annosum, whereas for Phanerochaete chrysosporium and the ECM fungi lower degradation rates were found. However, Paxillus involutus and S. bovinus showed comparable degradation rates at low concentrations of benzoic acid and 4-hydroxybenzoic acid. In contrast to liquid cultures, where no biodegradation of 3-CBA by S. bovinus was observed, mycorrhizal pines inoculated with S. bovinus showed a low capability to remove 3-CBA from soil substrates. Additional X-ray microanalytical investigations showed, that 3-CBA supplied to mycorrhizal plants was accumulated in the root cell cytoplasm and is translocated across the endodermis to the shoot of mycorrhizal pine seedlings.     

Occurrence of the carcinogenic Bracken constituent ptaquiloside in fronds,topsoils and organic soil layers in Denmark

Bracken (Pteridium aquilinum (L.) Kuhn) is a common fern found on all continents except Antarctica. It is under suspicion of causing cancer among people who utilizes it as food. The main carcinogenic compound is thought to be the water-soluble compound ptaquiloside. Ptaquiloside-uptake may occur not only through food, but also via drinking water as ptaquiloside might leach from plant material. The purpose of the study was to identify environmental parameters that correlate with the ptaquiloside-content in fronds, and to quantify the amount of ptaquiloside in the soil environment. The ptaquiloside-content in fronds, Oi/Oe-, and Oa/A-horizons was quantified at end of the growth season at 20 sites in Denmark. The fronds had ptaquiloside-contents between 108 and 3795 microgg(-1). The Oi/Oe-horizons had contents between 0.09 and 7.70 microgg(-1), while Oa/A-horizons had contents between 0.01 and 0.09 microgg(-1). The ptaquiloside-content in the standing biomass, which could be transferred to the soil by the end of the growing season, ranged between 10 and 260 mgm(-2), with nine sites having ptaquiloside loads over 100 mgm(-2). The carbon-content in the O-horizon, the precipitation, the amount of Bracken-litter, the turnover rate and the size of Bracken-stands determined the ptaquiloside-content in the soil materials while the content in fronds was found to be a function of the frond-height and the light-exposure in the ecosystem.     

Artificial indoor streams as a method to investigate the impact of chemicals on lotic communities

The potential hazard of chemicals on aquatic communities are generally evaluated by standardised single-species bioassays. Safety assessment is based on results gained from organisms adapted to lentic systems and biological interactions in ecosystems are neglected. While lotic communities are often at first in contact with chemicals, it is astonishing that microcosms with lentic communities are mainly used as a bridge between laboratory bioassays and outdoor aquatic systems. Hence, we established five artificial indoor streams to simulate abiotic factors of small rivers. The closed-circuit system was filled with nutrients added to tap water. Washed pebbles were used as sediment. The dynamics of a simple biocoenoses consisting of aufwuchs, Lumbriculus variegatus Asellus aquaticus and Gammarus fossarum was investigated. The dynamic of aufwuchs and periphyton was determined as dry weight and chlorophyll-a, respectively and qualitatively by pigment pattern. The abundance of different developmental stages of L. variegatus was determined at the end of the experiment as well as the population dynamics of G. fossarum and A. aquaticus. Survival rates of gammarids and juveniles per female were investigated and data were used for modelling the population dynamics. The experiment was carried out to investigate the performance of the established artificial streams and the developed approaches to investigate effects of chemicals on a basic lotic community. The prime reason to establish this approach was to close a gap between complex artificial stream systems and laboratory single species tests to assess the impact of chemicals on the aquatic environment.     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Reproduction and larval development in three scalpellid barnacles, Scalpellum scalpellum (Linnaeus 1767), Ornatoscalpellum stroemii (M. Sars 1859) and Arcoscalpellum michelottianum (Seguenza 1876), Crustacea: Cirripedia: Thoracica): implications for reproduction and dispersal in the deep sea

We studied reproduction and larval development in three species of pedunculated barnacles with different depth distribution, that is, Scalpellum scalpellum (30–200 m), Ornatoscalpellum stroemii (100–1,600 m) and Arcoscalpellum michelottianum (64–5,190 m). Morphology, position and number of males in the female/hermaphrodite, type of larval development and the number and size of eggs were recorded. All three species have a pair of pocket-like receptacles, each of which can host only a single male in O. stroemii, up to five males in S. scalpellum and up to 12 males in A. michelottianum. Eggs and larvae were smallest in S. scalpellum, intermediately sized in O. stroemii and largest in A. michelottianum. Brood size was comparable for S. scalpellum and O. stroemii, but five times higher in A. michelottianum. The ratio for body/egg size is almost similar in S. scalpellum and A. michelottianum, but much smaller in O. stroemii. Both S. scalpellum and A. michelottianum have nauplii that spend upwards of 10 days in the plankton while the larvae of O. stroemii hatch as cyprids that settle soon after release. All these reproductive data indicate that O. stroemii invests considerably more in each propagule than the other two species. We hypothesize that the observed differences in reproductive system and mode of development in the three species represent adaptations to their different habitats. S. scalpellum are mainly transported by currents in the coastal sublittoral zone. O. stroemii is presumably spread by intermediate deep currents along the shelf and shelf-slope, while A. michelottianum occurs on seamounts and is probably transported by demersal currents over wide areas of inhospitable soft-bottoms. Our observations are in accordance with the general pattern that, egg-size and propagule-size are positively correlated to bathymetric and geographic distribution, and that the continental slope environment represents a high disturbance environment, where a short larval stage is an advantage.