Recent advances in mercury speciation analysis with focus on spectrometric methods and enriched stable isotope applications

This paper discusses some recent advances in spectrometric methods and approaches for mercury speciation analysis of environmental samples with focus on isotope dilution techniques for determination of mercury species' concentrations in gaseous samples and reaction rates in soils and sediments. Such analytical data is important inter alia in fundamental research on mercury biogeochemistry and for risk assessments of mercury-contaminated soils and sediments and for designing effective remedial actions. The paper describes how the use of enriched stable isotope tracers in mercury speciation analysis can improve the traceability and accuracy of results, facilitate rational method developments, and be useful for studying biogeochemical processes, i.e. rate of reactions and fluxes, of mercury species. In particular the possibilities to study and correct for unwanted species transformation reactions during sample treatment and to study "natural" transformations of species in environmental samples, or micro- and mesocosm ecosystems, during incubations are highlighted. Important considerations to generate relevant data in isotope tracer experiments as well as reliability and quality assurance of mercury speciation analysis in general are also discussed.     

Taboos and forest governance: informal protection of hot spot dry forest in southern Madagascar

In the dry forest of southern Madagascar, a region of global conservation priority, formally protected areas are nearly totally absent. We illustrate how the continued existence of unique forest habitats in the Androy region is directly dependent on informal institutions, taboos, regulating human behavior. Qualitative interviews to map and analyze the social mechanisms underlying forest protection have been combined with vegetation analyses of species diversity and composition. Of 188 forest patches, 93% were classified as protected, and in Southern Androy all remaining forest patches larger than 5 ha were protected. Eight different types of forests, with a gradient of social fencing from open access to almost complete entry prohibitions, were identified. Transgressions were well enforced with strong sanctions of significant economic as well as religious importance. Analyses of species diversity between protected and unprotected forests were complicated because of size differences and access restrictions. However, since, for example, in southern Androy >90% of the total remaining forest cover is protected through taboos, these informal institutions represent an important, and presently the only, mechanism for conservation of the highly endemic forest species. We conclude that social aspects, such as local beliefs and legitimate sanctioning systems, need to be analyzed and incorporated along with biodiversity studies for successful conservation.     

Management options and effects on a marine ecosystem: assessing the future of the Baltic

We are using the coupled models in a decision support system, Nest, to evaluate the response of the marine ecosystem to changes in external loads through various management options. The models address all the seven major marine basins and the entire drainage basin of the Baltic Sea. A series of future scenarios have been developed, in close collaboration with the Helsinki Commission, to see the possible effects of improved wastewater treatment and manure handling, phosphorus-free detergents, and less intensive land use and live stocks. Improved wastewater treatment and the use of phosphorus-free detergents in the entire region would drastically decrease phosphorus loads and improve the marine environment, particularly the occurrence of cyanobacterial blooms. However, the Baltic Sea will remain eutrophic, and to reduce other effects, a substantial reduction of nitrogen emissions must be implemented. This can only be obtained in these scenarios by drastically changing land use. In a final scenario, we have turned 50% of all agricultural lands into grasslands, together with efficient wastewater treatments and a ban of phosphorus in detergents. This scenario will substantially reduce primary production and the extension of hypoxic bottoms, increase water transparency in the most eutrophied basins, and virtually eliminate extensive cyanobacterial blooms.     

The fate of isoproturon in a freshwater microcosm with Lemna minor as a model organism

Degradation, bioaccumulation and volatile loss of the 14C-labeled phenylurea herbicide isoproturon (IPU) was examined in a freshwater microcosm with the free floating macrophyte species Lemna minor during a 21-day exposure time. Isoproturon volatilisation was very low with 0.13+/-0.01% of the initially applied herbicide. Only a minor amount of the herbicide was completely metabolised, presumably by rhizosphere microorganisms and released as 14CO2. In total, about 9% isoproturon was removed from the aquatic medium during 21 days. The major portion of the pesticide was removed by bioaccumulation of Lemna minor (5.0+/-0.8%) and the bioconcentration factor (BCF) based on freshweight was 15.8+/-0.2. However, this study indicated a high persistence of IPU in freshwater ecosystems and a potential hazard due to bioaccumulation in non-target species. The novel experimental system of this study, developed for easy use and multiple sampling abilities, enabled quantitatively studying the fate of isoproturon and showed high reproducibility with a mean average (14)C-recovery rate of 97.1+/-0.7%.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil--Part II: PCB and PAH

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic bromeliad species as biomonitor and measuring bulk deposition rates of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). For the sum of PCB, overall deposition rates were between 17 and 314 ng/(m2 day) in winter and between 43 and 81 ng/(m2 day) in summer, respectively. Deposition rates of dioxin-like PCBs ranged from 0.14 to 2.8 pg WHO-TEQ/(m2 day) in winter and from 0.90 to 4.3 pg WHO-TEQ/(m2 day) in summer. PCB deposition rates (total PCB and WHO-TEQ) were in the same range in winter in V.R. and PNI. In summer, contamination levels in V.R. were 6-10-folds higher than in PNI. PCB concentrations in biomonitor samples from V.R. and PNI were in the same range in summer and in winter. Concentrations of total PCB ranged from 14 to 95 microg/kg dry matter (d.m.) in winter and from 18 to 27 microg/kg d.m. in summer, respectively. The TEQ values were between 1.7 and 4.1 ng WHO-TEQ/kg d.m. in winter and between 1.9 and 2.9 ng WHO-TEQ/kg d.m. in summer. PCB concentrations of di-ortho PCB but not of non-ortho PCB were a factor of 2-4 lower in summer in both areas. PCB congener profiles resembled those from technical formulations. The profiles shifted to the higher chlorinated congeners in summer, probable due to revolatilisation of the lighter components at higher temperatures. PCB profiles in biomonitor resembled those from deposition samples and the shift to the heavier congeners in summer was even more pronounced. PAH deposition rates were in a similar range in both areas (131-2415 ng/(m2 day)). PAH levels in biomonitor samples from V.R. were about one order of magnitude higher than in samples from PNI indicating the impact of local sources. PAH profiles revealed stationary thermal processes as main source of contamination in V.R. whereas in PNI, biomass burning seems to be the main contamination source.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Development and verification of a toxicokinetic model of polychlorinated biphenyl elimination in persons working in a contaminated building

BACKGROUND: Polychlorinated biphenyls are toxic and slowly degrading substances that have been in widespread industrial use in the 1960s and 1970s. Despite a worldwide reduction, environmental exposure remains an issue; the assessment of an individual's level of exposure at a given time in retrospect requires valid toxicokinetic modeling of the different PCB congeners. OBJECTIVES: To develop and verify a toxicokinetic model of the in vivo-degradation of PCB 28 and 52 in adult humans. METHODS: The plasma concentrations of PCB congeners were measured in 583 persons working in a contaminated building for an average of 14.7+/-9.6 years. The values were adapted to a simple pharmacokinetic model (yt = y0 x (1 - e(-kt))); the steady state concentration y0 was estimated based on the median values of persons working exposed more than 10 years. RESULTS: The steady state concentration of PCB 28 was 0.10 microg/l, that of PCB 52 0.02 microg/l. The half-life of the congeners was estimated based on a logarithmic regression analysis according to the model mentioned above; it was 2.18 (95% CI: 1.91-2.54) years for PCB 28 and 3.95 (95% CI: 3.55-4.45) years for PCB 52, respectively. Stepwise elimination of persons with very long employment duration did not reduce the estimated half-life. CONCLUSIONS: The estimated half-life is higher than previously published data especially for PCB 52. Possible reasons and implications of this finding are discussed.     

Comment on "Analysis of groundwater contamination using concentration-time series recorded during an integral pumping test: Bias introduced by strong concentration gradients within the plume" by Allelign Zeru and Gerhard Schäfer

We consider the results of a recent paper in this journal [Zeru, A. and Sch?fer, G., 2005. Analysis of groundwater contamination using concentration-time series recorded during an integral pumping test: Bias introduced by strong concentration gradients within the plume. Journal of Contaminant Hydrology 81 (2005) 106-124], which addresses the field-scale characterisation of contaminant plumes in groundwater. There, it is concluded that contaminant concentration gradients can bias Integral Pumping Test (IPT) interpretations considerably, in particular if IPTs are conducted in advective fronts of contaminant plumes. We discuss implications of this setting and also argue that the longitudinal and transverse dispersivities used in the examples of Zeru and Sch?fer (2005) of up to 30 m and 3 m, respectively, are generally very high for the here relevant capture zone scale (<20 m). However, regardless of both longitudinal and transverse concentration gradients, we further show through a counter-example that IPT results are unbiased as long as the concentration attenuation along the flow direction is linear over the capture zone extent.     

Plant senescence: a mechanism for nutrient release in temperate agricultural wetlands

The beneficial uptake of nutrients by wetland plants is countered to some extent by nutrient release back into the aquatic environment due to vegetative die-back. This current study examined whether Leersia oryzoides, a common wetland plant, exhibits luxury uptake of nutrients from simulated farm runoff. The study also tested whether with subsequent decomposition, these nutrients are released back into the water column. When exposed to elevated (>2mg/L N and P) runoff, L. oryzoides assimilated significantly higher concentrations of nitrogen (p<0.001) and phosphorus (p<0.001) in above-ground biomass as compared to non-enriched treatments (<0.05 mg/L N and P). Subsequently, senescence of enriched above-ground biomass yielded significantly higher concentrations of phosphorus (2.19+/-0.84 mg P/L). Using L. oryzoides as our model, this study demonstrates nitrogen and phosphorus sequestration during the growing season and release of phosphorus in the winter.     

Exemplifying whole-plant ozone uptake in adult forest trees of contrasting species and site conditions

Whole-tree O3 uptake was exemplified for Picea abies, Fagus sylvatica and Larix decidua in stands at high and low altitude and contrasting water availability through sap flow measurement in tree trunks, intrinsically accounting for drought and boundary layer effects on O3 flux. O3 uptake of evergreen spruce per unit foliage area was enhanced by 100% at high relative to low elevation, whereas deciduous beech and larch showed similar uptake regardless of altitude. The responsiveness of the canopy conductance to water vapor and, as a consequence, O3 uptake to soil moisture and air humidity did not differ between species. Unifying findings at the whole-tree level will promote cause-effect based O3 risk assessment and modeling.