Effectiveness of different pre-treatments in recovering pre-burial isotopic ratios of charred plants.

RATIONALE: Isotopic analysis of archaeological charred plant remains offers useful archaeological information. However, adequate sample pre-treatment protocols may be necessary to provide a contamination-free isotopic signal while limiting sample loss and achieving a high throughput. Under these constraints, research was undertaken to compare the performance of different pre-treatment protocols. METHODS: Charred archaeological plant material was selected for isotopic analysis (δ13 C and δ15 N values) by isotope ratio mass spectrometry from a variety of plant species, time periods and soil conditions. Preservation conditions and the effectiveness of cleaning protocols were assessed through Fourier transform infrared spectroscopy and X-ray fluorescence (XRF) spectrometry. An acid-base-acid protocol, successfully employed in radiocarbon dating, was used to define a contamination-free isotopic reference. Acid-base-acid isotopic measurements were compared with those obtained from untreated material and an acid-only protocol. RESULTS: The isotopic signals of untreated material and the acid-only protocol typically did not differ more than 1‰ from those of the acid-base-acid reference. There were no significant isotopic offsets between acid-base-acid and acid-only or untreated samples. Sample losses in the acid-base-acid protocol were on average 50 ± 17% (maximum = 98.4%). Elemental XRF measurements showed promising results in the detection of more contaminated samples albeit with a high rate of false positives. CONCLUSIONS: For the large range of preservation conditions described in the study, untreated charred plant samples, water cleaned of sediments, provide reliable stable isotope ratios of carbon and nitrogen. The use of pre-treatments may be necessary under different preservation conditions or more conservative measurement uncertainties should be reported.

Factors controlling the oral bioaccessibility of anthropogenic Pb in polluted soils.

In human risk assessment, ingestion of soil is considered a major route of toxic Pb exposure. A large body of research has focussed on the measurement of the 'total' Pb contents in sediment, soil and dust as a measure for the exposure to lead. We report that Pb bioaccessibility (i.e. the maximum bioavailability), determined with an in vitro test, does not necessarily depend on the total Pb content. In contrast, the Pb bioaccessibility is initially controlled by the chemical form and particle size of the Pb source, which in turn determine its solubility. Furthermore, when anthropogenic Pb resides within the soil, it may form new, more stable, minerals and/or binds to organic matter, clay, reactive iron or other reactive phases, changing its bioaccessibility. The bioaccessible Pb fraction of 28 soils, polluted with various Pb sources (including residues of Pb bullets and pellets, car battery Pb, city waste and diffuse Pb), was determined with an in vitro-test and varied from 0.5% to 79.0% of total Pb. The highest Pb bioaccessibility (60.7% to 79.0%) was measured in soils polluted with residues of Pb bullets and pellets (shooting range), while the lowest Pb bioaccessibility (0.5%-8.3%) was measured in soils polluted with city waste (including remnants of Pb glazed potsherds and rooftiles, Pb based paint flakes, and Pb sheets). Bioaccessibility of Pb was correlated with pH, organic matter and reactive Fe. These results indicate that soil characteristics play an important role in the oral bioaccessibility of lead in polluted soils. Instead of basing human risk assessment solely on total Pb contents we propose to incorporate in vitro bioaccessibility tests, taking factors such as soil pH, organic matter content and reactive iron content into account. This approach will result in a better insight into the actual risks of Pb polluted soils to children.

Reconstruction of historical atmospheric Pb using Dutch urban lake sediments: a Pb isotope study.

Lake sediments provide a record of atmospheric Pb deposition and changes in Pb isotope composition. To our knowledge, such an approach has not previously been performed in The Netherlands or linked to national air monitoring data. Results are presented for Pb content and isotope composition of (137)Cs dated lake sediments from 2 Dutch urban lakes. Between 1942 and 2002A.D. anthropogenic atmospheric Pb deposition rates in the two lakes varied from 12±2 to 69±16µgcm(-2)year(-1). The rise and fall of leaded gasoline is clearly reflected in the reconstructed atmospheric Pb deposition rates. After the ban on leaded gasoline, late 1970s/early 1980s, atmospheric Pb deposition rates decreased rapidly in the two urban lakes and the relative contributions of other anthropogenic Pb sources - incinerator ash (industrial Pb) and coal/galena - increased sharply. Atmospheric Pb deposition rates inferred from the lake record a clear relationship with nearby measured annual mean air Pb concentrations. Based on this relationship it was estimated that air Pb concentrations between 1942 and 2002A.D. varied between 5 and 293ng/m(3).

The lead (Pb) isotope signature, behaviour and fate of traffic-related lead pollution in roadside soils in The Netherlands.

In this study the origin, behaviour and fate of anthropogenic Pb in sandy roadside soils were assessed by measuring soil characteristics, Pb isotope composition and content. In 1991 and 2003 samples were taken at different depth intervals at approximately 8 and 75 m from two highways in The Netherlands. The Pb isotope composition of the litter layer ((206)Pb/(207)Pb=1.12-1.14) differs from the deeper soil samples ((206)Pb/(207)Pb=1.20-1.21). Based on a mixing model it is concluded that the samples contain two Pb sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. (206)Pb/(207)Pb ratios demonstrate that the roadside soils were polluted to a depth of ~15 cm. Within this depth interval, anthropogenic Pb content is associated with organic matter. Although Pb pollution only reached a depth of ~15 cm, this does not mean that the topsoils retain all anthropogenic Pb. Due to the low pH and negligible binding capacity of soils at depths >15 cm, anthropogenic Pb migrated towards groundwater after reaching depths of >15 cm. The Pb isotope composition of the groundwater ((206)Pb/(207)Pb=1.135-1.185) establishes that groundwater is polluted with anthropogenic Pb. The contribution of anthropogenic Pb to the groundwater varies between ~30 and 100%. Based on the difference in soil Pb content and Pb isotope compositions over a period of 12 years, downward Pb migration is calculated to vary from 72 ± 95 to 324 ± 279 mg m(-2)y(-1). Assuming that the downward Pb flux is constant over time, it is calculated that 35-90% of the atmospherically delivered Pb has migrated to the groundwater.

Genetic structure in populations of an ancient woodland sedge, Carex sylvatica Hudson, at a regional and local scale.

Wood sedge (Carex sylvatica) is a well-known ancient woodland species with a long-term persistent seed bank and a caespitose growth habit. All thirteen isolated Carex sylvatica populations in the Dutch Rhine floodplain (including the river branches Waal and IJssel) were mapped in detail and analysed for genetic variation at a large number of AFLP loci and one microsatellite locus. Across all populations, only 40 % of the sampled individuals (n=216) represented a unique genotype. A high number of the studied patches (spatial clusters of tussocks, 2-10 m in diameter) within populations contained only one or a few genotypes. Identical plants (tussocks) were also found 20-500 m apart and in one case even 1000 m apart. Observed heterozygosity levels (H(O)=0.029) were low, indicating low levels of gene flow, which is in agreement with the selfing nature of other caespitose sedges. Although the number of genotypes in populations is low, these genotypes are genetically very distinct and variation within populations accounted for 55% of the total variation. The absence of a correlation between genetic and geographic distances among populations, and the scattered distribution of genotypes among patches within woodlands, support our hypothesis of rare establishments and subsequent local dispersal within woodlands in this forest floor species, which may benefit from and partly depend on human land use and forest management activities.

Calibration of lichen transplants considering faint memory effects.

Biomonitoring, among other purposes, can be used as a tool to study the dispersion of trace elements through the atmosphere and back to the earth's surface again. In this sense it has been used for more than 20 years now. Yet, the calibration of biomonitors elemental contents against other atmospheric element dispersion variables like deposition or airborne concentration is still an open subject. The knowledge of a calibration nevertheless represents a qualitative improvement upon the use of biomonitors. Biomonitors elemental contents are usually assumed to depend in a linear way on the average values of atmospheric element dispersion variables, thus a linear regression is assumed to provide a good calibration. In this work: the element dispersion variables like deposition or airborne concentration will be referred in general as availability variables due to reasons that will be clarified; an uptake experiment using transplants of lichen Parmelia sulcata carried out in Portugal during a 2-year period (1994/1996) is described; and new concepts and calibration methods are presented. Lichen and aerosol samples were analysed by nuclear analytical techniques PIXE and INAA, and total deposition dry residue samples were analysed by ICP-MS. A database of roughly 70,000 values was thus created and biomonitor calibration carried out considering that biomonitors are not mechanical instruments but that they rather describe their exposure with a non-perfect memory. Data shows that surveying lichens four times within 1 year, with a period of 3 months in between sampling campaigns, allows the recovery of availability mean, maxima and standard deviation for many elements.

Possible relevance of pigeons as an indicator species for monitoring air pollution.

Wild city pigeons were caught at four different locations in the Netherlands to represent areas of high (Amsterdam-high), moderate (Amsterdam-medium), and low (Maastricht and Assen) traffic density. It is assumed that local ambient air pollution decreases as a function of traffic density. In these pigeons levels of polycyclic aromatic hydrocarbon (PAH)-DNA adducts, oxidative DNA damage, and heavy metal residues were determined in kidney, lung, liver, and blood (no adduct analysis in blood). The contribution of leaded gasoline to total body lead content was estimated by measuring concentrations of Pb and its isotopes in blood. We also analyzed samples of ambient air particulate matter for PAH and heavy metal concentrations at the four different locations. Interregional differences in heavy metals in ambient air particulate matter were reflected relatively well by pigeon body loads. The higher lead and cadmium concentrations in blood, kidney, liver, and lung were found in the Amsterdam high traffic density area, followed by Amsterdam medium, Assen, and Maastricht. A high Pb concentration in blood coincided with relatively low 206Pb/207Pb values, indicating a high contribution of leaded gasoline to total blood Pb concentrations in pigeons from the Amsterdam high traffic density area. Significantly enhanced blood zinc values were found in pigeons from both locations in Amsterdam compared to pigeons from the other two areas. However, no differences in Zn tissue levels between the four different groups were found. Oxidative DNA damage, determined as the ratio of 7-Hydro-8-oxo-2'-deoxyguanosine/ deoxyguanosine, in pigeon liver was highest in Amsterdam-high, followed by Assen (low traffic density). Pb content, but not the Cd content, was positively associated with oxidative DNA damage in liver tissue. In lung tissue, a negative correlation was found between oxidative DNA damage and Zn content. These results indicate that the carcinogenic potential of Pb might be ascribed to oxygen radical formation, whereas Zn plays a protective role against oxidative DNA damage. Places with high and medium traffic density could be clearly discriminated on the basis of PAH levels in the ambient air. The PAH content in particulate air samples was not, however, reflected in total PAH-related DNA adduct levels because no differences could be observed in tissue adduct levels in pigeons from the four different locations. Our results indicate that wild city pigeons can be used as biological indicators of exposure to heavy metal pollution in outdoor air.