The physico-chemical absorption characteristics of ammonium-N for 10 soils from 5 profiles in York, UK, show its high potential mobility in N deposition-impacted, unfertilized, permanent grassland soils. Substantial proportions of ammonium-N inputs were retained in the solution phase, indicating that ammonium translocation plays an important role in the N cycling in, and losses from, such soils. This conclusion was further supported by measuring the ammonium-N leaching from intact plant/soil microcosms. The ammonium-N absorption characteristics apparently varied with soil pH, depth and soil texture. It was concluded for the most acid soils especially that ammonium-N leached from litter horizons could be seriously limiting the capacity of underlying soils to retain ammonium. Contrary to common opinion, more attention therefore needs to be paid to ammonium leaching and its potential role in biogeochemical N cycling in semi-natural soil systems subject to atmospheric pollution. mmonium mobility is more important than previously thought in N-impacted, unfertilized grasslands.

Polycyclic aromatic hydrocarbons (PAHs) comprise an important group of air pollutants, with three-ring components (PAH-3) often dominating. Spatiotemporal variation in atmospheric PAH-3 can be analyzed by biomonitoring but high vapour pressure and low octanol-air-partitioning of PAH-3 cause dynamic accumulation on plant surfaces. This study for the first time shows that PAH-3 exhibit systematic accumulation trends on pine needles of 3-48 months of exposure time at six sites in Germany. Correlation of needle exposure time with PAH-3 concentration was r² = 0.83 for phenanthrene and methylphenanthrenes, r² = 0.77 for cyclopenta[def]phenanthrene, r² = 0.60 for dibenzothiophene, r² = 0.57 for dimethylphenanthrenes and r² = 0.32 for retene. Variations in PAH-3 for summer and winter collected needles emphasize vegetation-air-partitioning influence on cumulative PAH-3 loads. PAH-3 ratios calculated for needle cohorts indicate persistence of original PAH patterns thus demonstrating the source-diagnostic potential of pine needle biomonitoring, which is utilized in part II of this study where spatial distribution of PAH-3 is investigated and related to emission sources. Accumulation of volatile three-ring PAHs on pine needles was found to be systematic over a period of 50 months thus qualifying PAHs for regional air quality studies.

This seven-year survey was primarily targeted to quantification of production of nodularin-R (NOD-R), a cyclic pentapeptide hepatotoxin, in Baltic Sea cyanobacteria waterblooms. Additionally, NOD-R and microcystin-LR (MC-LR; a cyclic heptapeptide toxin) sedimentation rates and NOD-R sediment storage were estimated. NOD-R production (70-2450 μg m⁻³; 1 kg km⁻² per season) and sedimentation rates (particles; 0.03-5.7 μg m⁻² d⁻¹; 0.3 kg km⁻² per season) were highly variable over space and time. Cell numbers of Nodularia spumigena did not correlate with NOD-R quantities. Dissolved NOD-R comprised 57-100% of total NOD-R in the predominantly senescent, low-intensity phytoplankton blooms and seston. Unprecedentedly intensive MC-LR sedimentation (0.56 μg m⁻² d⁻¹) occurred in 2004. Hepatotoxin sedimentation rates highly exceeded those of anthropogenic xenobiotics. NOD-R storage in surficial sediments was 0.4-20 μg kg⁻¹ (0.1 kg km⁻²). Loss of NOD-R within the chain consisting of phytoplankton, seston and soft sediments seemed very effective. Production of nodularin-R in pelagic Baltic Sea takes place in a scale of up to kilograms per square kilometre.

A solid-phase microextration-based sampling method was employed to determine the concentrations of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (DDE) and 1-chloro-2,2-bis(p-chlorophenyl)ethene (DDMU), in two estuarine bays, Daya Bay and Hailing Bay, of South China. Six DDT components including p,p'-DDT, o,p'-DDD, p,p'-DDD, o,p'-DDE, p,p'-DDE, and p,p'-DDMU were detected in Hailing Bay, while only p,p'-DDD was found in Daya Bay. p,p'-DDD was the most abundant DDT component in both bays, sharply different from the previous finding in the water column of the Palos Verdes Shelf, California, USA that p,p'-DDE was prevalent. In addition, the occurrence of p,p'-DDMU (with a range of 0.047-0.21 ng/L in Hailing Bay) has not been reported around the globe, and its presence in our study region appeared to stem from dehydrochlorination of p,p'-DDD, favored under aerobic conditions, but further investigations are clearly needed to confirm the mechanism for generation of DDMU in estuarine environments. DDT and its metabolites, particularly p,p'-DDMU, are detected in the water column of two estuarine bays in South China using a SPME-based sampler.

Fluoroquinolones like difloxacin (DIF) and sarafloxacin (SARA) are adsorbed in soil and enter the aquatic environment wherein they are subjected to photolytic degradation. To evaluate the fate of DIF and SARA, their photolysis was performed in water under stimulated natural sunlight conditions. DIF primarily degrades to SARA. On prolonged photodegradation, seven photoproducts were elucidated by HR-LC-MS/MS, three of which were entirely novel. The residual anti-bacterial activities of DIF, SARA and their photoproducts were studied against a group of pathogenic strains. DIF and SARA revealed potency against both Gram-positive and -negative bacteria. The photoproducts also exhibited varying degrees of efficacies against the tested bacteria. Even without isolating the individual photoproducts, their impact on the aquatic environment could be assessed. Therefore, the present results call for prudence in estimating the fate of these compounds in water and in avoiding emergence of resistance in bacteria caused by the photoproducts of DIF and SARA.

Soil was spiked with [9-¹⁴C]phenanthrene and [1-¹⁴C]hexadecane at 50 mg kg⁻¹ and aged for 1, 25, 50, 100 and 250 d. At each time point, the microcosms were amended with aqueous solutions of cyclodextrin (HP-β-CD) at a range of concentrations (0-40 mM). Mineralisation assays and aqueous HP-β-CD extractions were performed to assess the effect of the amendments on microbial degradation. The results showed that amendments had no significant impact on the microbial degradation of either of the ¹⁴C-contaminants. Further, HP-β-CD extractions were correlated with the mineralisation of the target chemicals in each of the soil conditions. It was found that the HP-β-CD extraction was able to predict mineralisation in soils which had not been amended with cyclodextrin; however, in the soils containing the HP-β-CD, there was no predictive relationship. Under the conditions of this study, the introduction of HP-β-CD into soils did not enhance the biodegradation of the organic contaminants. The amendment of HP-β-CD to phenanthrene and hexadecane amended soils does not enhance microbial biodegradation.

Bioavailability of Cu in the soil is a function of its speciation. In this paper we investigated Cu speciation in six soils using X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and synchrotron-based micro X-ray fluorescence (μ-XRF). The XANES and EXAFS spectra in all of the soils were the same. μ-XRF results indicated that the majority of the Cu particles in the soils were not associated with calcium carbonates, Fe oxides, or Cu sulfates. Principal component analysis and target transform of the XANES and EXAFS spectra suggested that Cu adsorbed on humic acid (HA) was an acceptable match. Thus it appears that Cu in all of the soils is primarily associated with soil organic matter (SOM). Theoretical fitting of the molecular structure in the soil EXAFS spectra revealed that the Cu in the soils existed as Cu atoms bound in a bidentate complex to O or N functional groups.

We examined the effect of ozone (O₃) on Norway spruce (Picea abies) needle epicuticular wax over three seasons at the Kranzberg Ozone Fumigation Experiment. Exposure to 2x ambient O₃ ranged from 64.5 to 74.2 μl O₃ l⁻¹ h AOT40, and 117.1 to 123.2 nl O₃ l⁻¹ 4th highest daily maximum 8-h average O₃ concentration. The proportion of current-year needle surface covered by wax tubes, tube aggregates, and plates decreased (P = 0.011) under 2x O₃. Epistomatal chambers had increased deposits of amorphous wax. Proportion of secondary alcohols varied due to year (P = 0.004) and O₃ treatment (P = 0.029). Secondary alcohols were reduced by 9.1% under 2x O₃. Exposure to 2x O₃ increased (P = 0.037) proportions of fatty acids by 29%. Opposing trends in secondary alcohols and fatty acids indicate a direct action of O₃ on wax biosynthesis. These results demonstrate O₃-induced changes in biologically important needle surface characteristics of 50-year-old field-grown trees. Free-air ozone exposure induced changes in needle wax characteristics of mature Picea abies.

The response of specific groups of organisms, like Collembola to atmospheric nitrogen (N) deposition is still scarcely known. We investigated the Collembola community in a subalpine forest (Alptal, Switzerland) as subjected for 12 years to an experimentally increased N deposition (+25 on top of ambient 12 kg N ha⁻¹ year⁻¹). In the 0-5 cm soil layer, there was a tendency of total Collembola densities to be lower in N-treated than in control plots. The density of Isotomiella minor, the most abundant species, was significantly reduced by the N addition. A tendency of lower Collembola group richness was observed in N-treated plots. The Density-Group index (dDG) showed a significant reduction of community diversity, but the Shannon-Wiener index (H') was not significantly affected by the N addition. The Collembola community can be considered as a bioindicator of N inputs exceeding the biological needs, namely, soil N saturation. Collembola community, which was significantly affected by a long-term N addition experiment, can be considered as a bioindicator of N saturation.

Bacteria from this soil were cultured in mineral salt solution supplemented with mesotrione as sole source of carbon for the isolation of mesotrione-degrading bacteria. The bacterial community structure of the enrichment cultures was analyzed by temporal temperature gradient gel electrophoresis (TTGE). The TTGE fingerprints revealed that mesotrione had an impact on bacterial community structure only at its highest concentrations and showed mesotrione-sensitive and mesotrione-adapted strains. Two adapted strains, identified as Bacillus sp. and Arthrobacter sp., were isolated by colony hybridization methods. Biodegradation assays showed that only the Bacillus sp. strain was able to completely and rapidly biotransform mesotrione. Among several metabolites formed, 2-amino-4-methylsulfonylbenzoic acid (AMBA) accumulated in the medium. Although sulcotrione has a chemical structure closely resembling that of mesotrione, the isolates were unable to degrade it. A Bacillus sp. strain isolated from soil was able to completely and rapidly biotransform the triketone herbicide mesotrione.