Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Atmospheric deposition of silver and thallium since 12 370 14C years BP recorded by a Swiss peat bog profile, and comparison with lead and cadmium

A peat core from an ombrotrophic bog in Switzerland provides the first complete, long-term record (14 500 years) of atmospheric Ag and Tl deposition. The lack of enrichment of Ag and Tl in the basal peat layer shows that mineral dissolution in the underlying sediments has not contributed measurably to the Ag and Tl inventories in the peat column, and that Ag and Tl were supplied exclusively by atmospheric deposition. The temporal and spatial distribution of modern peaks in Ag and Tl concentrations are similar to those of Pb which is known to be immobile in peat profiles. Silver and Tl, therefore, are effectively immobile in the peat bog also, allowing an atmospheric deposition chronology to be reconstructed. Silver concentrations vary by up to 114x and Tl up to 241x. While Holocene climate change and land use history can explain the variation in metal concentrations and enrichment factors (EF) in ancient peats (i.e. pre-dating the Roman Period), anthropogenic sources have to be invoked to explain the very high EF values (up to 123 in the case of Ag and 12 in the case of Tl) in peat samples since the middle of the 19th Century. The "natural background" EF of Tl in ancient peats is remarkably close to unity, indicating a lack of significant enrichment of this element in atmospheric aerosols due to chemical weathering of crustal rocks. Silver, on the other hand, shows a pronounced enrichment from 8030 to 5230 (14)C years BP (12x compared to crustal rocks); this may be due to weathering phenomena or biological processes, both of which are driven by climate. Even compared to the natural enrichment of Ag during the mid-Holocene, however, the enrichments of Ag and Tl in modern peats from the Industrial Period are at least an order of magnitude greater. The Pb/Ag and Tl/Ag ratios show that Pb and Tl are preferentially released, compared to Ag, during smelting of argentiferous Pb ores mined during the Roman and Medieval Periods.     

Review of ozone and temperature lidar validations performed within the framework of the Network for the Detection of Stratospheric Change

The use of assimilation tools for satellite validation requires true estimates of the accuracy of the reference data. Since its inception, the Network for Detection of Stratospheric Change (NDSC) has provided systematic lidar measurements of ozone and temperature at several places around the world that are well adapted for satellite validations. Regular exercises have been organised to ensure the data quality at each individual site. These exercises can be separated into three categories: large scale intercomparisons using multiple instruments, including a mobile lidar; using satellite observations as a geographic transfer standards to compare measurements at different sites; and comparative investigations of the analysis software. NDSC is a research network, so each system has its own history, design, and analysis, and has participated differently in validation campaigns. There are still some technological differences that may explain different accuracies. However, the comparison campaigns performed over the last decade have always proved to be very helpful in improving the measurements. To date, more efforts have been devoted to characterising ozone measurements than to temperature observations. The synthesis of the published works shows that the network can potentially be considered as homogeneous within +/-2% between 20-35 km for ozone and +/-1 K between 35-60 km for temperature. Outside this altitude range, larger biases are reported and more efforts are required. In the lower stratosphere, Raman channels seem to improve comparisons but such capabilities were not systematically compared. At the top of the profiles, more investigations on analysis methodologies are still probably needed. SAGE II and GOMOS appear to be excellent tools for future ozone lidar validations but need to be better coordinated and take more advantage of assimilation tools. Also, temperature validations face major difficulties caused by atmospheric tides and therefore require intercomparisons with the mobile systems, at all sites.     

Biological responses of workplace particles and their association with adverse health effects on miners

Epidemiological research has demonstrated the relationship between exposure to quartz dust and an elevated risk of pneumoconiosis and possible elevated risk of cancer. The current study was designed to evaluate the biological responses of workplace particles containing crystalline silica using an in vitro cell test. Respirable particle samples were sampled from four tin mines, where the standardized mortality ratio (SMR) for pneumoconiosis was 51.6 and SMR for lung cancer was 2.2 in dust-exposed miners. Alveolar macrophages (AM) are considered as the target cells for primary dust effects. The samples were then measured at 15, 30, 60 and 120 microg particle per 10(6) AM for cytoxicity with the release of glucuronidase, lactate dehydrogenase, for reactive oxygen damage with H(2)O(2) release, and for ability to induce fibrosis using the secretion of tumor necrosis factor-alpha (TNF-alpha). Pure quartz (DQ12) and corundum were used as controls. The results showed the samples from tin mines caused a higher cytoxicity when compared to corundum, yet lower when compared to quartz. However, reactive oxygen species release (148-177 nmol/3 x 10(5) AM in high concentration of 120 microg/10(6) AM) induced by the samples were significantly higher than that induced by quartz (57 nmol/3 x 10(5) AM) and corundum (62 nmol/3 x 10(5) AM). Furthermore, particle samples induced higher TNF-alpha secretion than corundum, the samples from Limu tin mine induced much higher TNF-alpha levels than that induced by DQ12 quartz. The results from the in vitro tests help elucidate the degree of hazard of dust particles in tin mines. The in vitro reaction patterns of AM also constitute a powerful tool to monitor biological and pathogenic responses of humans following dust particle exposure.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Natural and man-made organobromine compounds in marine biota from Central Norway

Brominated organic pollutants were found in selected samples of mollusk tissue, fish liver, as well as in the eggs and livers of shag from three sites in Central Norway. More than 80 organobromines were identified owing to the defined isotope ratio acquired by GC/ECNI-MS. However, only a few peaks could be assigned to anthropogenic brominated flame retardants (polybrominated diphenyl ethers). Most of the organobromine compounds detected were unknown or halogenated natural products. The known halogenated natural products MHC-1 and TBA were abundant in all samples and usually between equally abundant, and up to 50 fold more concentrated than the major polybrominated diphenyl ether congener BDE 47. The halogenated natural products BC-2 (2-MeO-BDE 68) and BC-3 (6'-MeO-BDE 47), were on level with BDE 100 which was the second most abundant BDE congener in many samples. The previously identified natural polybrominated hexahydroxanthene derivatives (PBHDs) were detected for the first time in bird eggs. Being major contaminants in bird eggs, PBHDs were only present at low levels in bird liver from nestlings originating from the same clutch. Such differences were detected for several other major contaminants. One unknown tetrabromo compound particularly abundant in mussels from Munkholmen was studied by GC/MS and the molecular ion was detected at m/z 446. The abundance of the most important unknown compounds did not correlate with BDEs and they most likely represent halogenated natural products. This study supports that halogenated natural products have to be treated as serious contaminants of marine coastal waters. Our data suggest that their abundance is highest in habitats along the shoreline. Thorough examination of these compounds in environmental samples is an important task.     

Risk assessment on disinfection by-products of drinking water of different water sources and disinfection processes

The occurrences of trihalomethanes (THMs) and haloacetics (HAAs) in the water supply in Beijing and Canada were investigated. The concentrations of THMs and HAAs in Beijing and Canada were below the maximum contaminant levels specified by the USEPA and WHO standards. The multi-pathway risk assessment (assessed through oral ingestion, dermal absorption and inhalation exposure to drinking water) was used to assess the cancer risk and the hazard index of THMs and HAAs from fifteen waterworks in Beijing, China and three treatment plants using different disinfection processes in Canada. Residents in Beijing and residents who were served by three treatment plants using different disinfection processes in Canada had a higher risk of cancer through oral ingestion than through the other two pathways. The cancer risk resulted from disinfection by-products (DBPs) was 8.50E-05(for males), 9.25E-05(for females) in Beijing, China, while it was 1.18E-04, 1.44E-04 in Canada. The risk was higher when water treatment plants used surface water source than when they used ground water source and mixture water source in Beijing. The risk showed different changes in three treatment plants using different disinfection processes in Canada. The lifetime cancer risk for THMs followed the order: Plant 2>Plant 1>Plant 3. And, the lifetime cancer risk for HAAs was: Plant 1>Plant 2>Plant 3.     

Intra-cultivar variability of the soil-to-grain transfer of fallout 137Cs and 90Sr for winter wheat

Differences between the root uptake of fallout radionuclides by different cultivars ('inter-cultivar' variability) growing on the same field may be influenced not only by genetic differences of the cultivars, but also by the spatial variability of the soil-to-grain transfer within the cultivation area of each cultivar. This 'intra-cultivar' variability was investigated in 2001 and 2002 for 137Cs and 90Sr using three winter wheat cultivars with four replicates for each cultivar at three different sites in Bavaria, Germany. The intra-cultivar variability proved to be in the same range as the inter-cultivar variability which was determined earlier at the same sites for both radionuclides. An ANOVA of the 137Cs data set revealed that the variability of the 137Cs soil-to-grain transfer was caused by the soil and climate (year) at the field sites and the interaction of cultivar and field. A significant contribution of the factor 'cultivar' alone to the variability could not be detected. This may be due to the complex environmental conditions to which plants are exposed in field experiments. To find wheat cultivars with minimal uptake of fallout radionuclides it may be better to examine the molecular mechanisms of their root uptake in order to identify targets for breeding "safer" plants.     

Soil erosion and its impacts on water treatment in the northeastern provinces of Thailand

The economy of Northeast Thailand is mainly based on agriculture. The transformation of forestlands to agricultural areas and the encroachment of riverbanks within the Phong watershed have caused severe soil erosion. Strong storms in rainy season exacerbate the problem of soil erosion. Difficulty in getting water drives people in the upstream region to live on riverbanks. Soil erosion affects water utility by increasing the turbidity in the Phong River and also by decreasing the water storage capacity of small reservoirs for the upstream residents, as well as that of the Ubolratana Dam. The rate of siltation in the Ubolratana Dam was estimated to be 1.5 million tons/year during 1965-1990. The main source of water supply is surface water in the Phong watershed, and fluctuating turbidity makes water treatment difficult. The maximum turbidity in the upstream Phong River exceeds 5000 NTU, whereas it is reduced to be about 300 NTU at the intake point of Khon Kaen Municipal Water Treatment Plant because the Ubolratana Dam works as a huge clarifier. Khon Kaen Municipal Waterworks has a daily water supply of 72,960 m3/day. The average amounts of alum used in the wet (May-October) and dry (November-April) periods are 42.33 g/m3 and 28.46 g/m3, respectively. The average costs of the amounts of alum used are 0.213 and 0.143 Bahts/m3 during the wet and dry periods, respectively. Fluctuation of turbidity in raw water makes it difficult to adjust alum dose, resulting in treated water quality unstable, and handling of sludge disposal difficult.     

Trace element levels in foetus-mother pairs of short-beaked common dolphins (Delphinus delphis) stranded along the French coasts

Tissues of foetus-mother pairs of common dolphins (Delphinus delphis) stranded along the French coasts (Bay of Biscay and English Channel) were analysed for their Cd, Cu, Hg, Se and Zn contents. In the kidneys, foetal Cd levels were extremely low, and strong relationships between Cu and Zn suggested the involvement of metallothioneins since early foetal life. The results also indicated a limited maternal transfer of Hg during pregnancy since levels in the tissues of foetuses were below 1 microg g(-1) w.wt. However, hepatic Hg levels in foetuses increased with body length, and were also proportionate to maternal hepatic, renal and muscular Hg levels. Lastly, affinities between Hg and Se in tissues would participate in Hg neutralisation in both mothers--through tiemannite granules--and fetuses--through reduced glutathione--counteracting the toxic effects linked to the particularly high quantities of methyl-Hg to which marine mammals are naturally exposed.