Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations

The production of N₂ gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of ³H/³He, CFCs and SF₆ as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R² = 69%), as well as the ³H (R² = 79%) and ³He (R² = 76%) concentrations observed in a ³H/³He data set using simple 2D models. We found that the TDG correction of the ³H/³He age overestimated the control ³He/³He age by 2.1 years, due to the accumulation of ³He in the gas phase. The total uncertainty of degassed ³H/³He ages of 6 years (± 2 σ) is due to the correction of degassed ³He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak ³He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF₆ is highly susceptible to degassing. We conclude that ³H/³He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.     

Impact of mineral components and selected trace metals on ambient PM10 concentrations

PM10 levels of the mineral components Si, Al, Fe, Ca, Mg and some trace metals were measured at three different sites in the urban area of Vienna (Austria). Observed trace metal concentrations varied between less than 0.1 ng m^?3 (Cd) and approximately 200 ng m^?3 (Zn), mineral components showed enhanced concentrations ranging from 0.01 μg m^?3 (Ca) to 16.3 μg m^?3 (Si). The contribution of the respective mineral oxides to PM10 mass concentrations accounted on average for 26.4 ± 16% (n = 1090) of the PM10 mass, with enhanced rates in spring and autumn (monthly averages of up to 40%) and decreased contributions in the cold season (monthly averages below 10%). The atmospheric occurrence of Al, Ti and Sr could be assigned to crustal sources, whereas for the elements Ba, Ca, Fe, Mg, Mn and V an increased contribution of non-crustal origin was observed. PM10 levels of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn and Zn were predominantly derived from man-made emissions. Intersite comparison indicated that urban PM10 mass concentrations and PM10 levels of As, Pb and Zn were predominantly influenced from the transport of aerosols from outside into the city, whereas for the elements Ba, Mg, Ca, Cu and Fe a distinctly increased impact of local emissions was observed. The contribution of these urban emissions to total PM10 concentrations was estimated by calculating the so-called “urban impact”, which was found to be 32.7 ± 18% (n = 392) in the case of PM10 mass concentrations. The investigated elements accounted on average for 31.3 ± 19% (n = 392) of the observed PM10 mass increase. The mean values for the “urban impacts” of individual elements varied between 25.5% (As) and 77.0% (Ba).     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Particles in swimming pool filters--does pH determine the DBP formation?

The formation was investigated for different groups of disinfection byproducts (DBPs) during chlorination of filter particles from swimming pools at different pH-values and the toxicity was estimated. Specifically, the formation of the DBP group trihalomethanes (THMs), which is regulated in many countries, and the non-regulated haloacetic acids (HAAs) and haloacetonitriles (HANs) were investigated at 6.0≤pH≤8.0, under controlled chlorination conditions. The investigated particles were collected from a hot tub with a drum micro filter. In two series of experiments with either constant initial active or initial free chlorine concentrations the particles were chlorinated at different pH-values in the relevant range for swimming pools. THM and HAA formations were reduced by decreasing pH while HAN formation increased with decreasing pH. Based on the organic content the relative DBP formation from the particles was higher than previously reported for body fluid analogue and filling water. The genotoxicity and cytotoxicity estimated from formation of DBPs from the treated particle suspension increased with decreasing pH. Among the quantified DBP groups the HANs were responsible for the majority of the toxicity from the measured DBPs.     

Evidence for Acidification-Driven Ecosystem Collapse of Danish Erica tetralix Wet Heathland

We report observations of disappearance of Erica tetralix in wet heathland, which is unlikely to be caused by competition, as E. tetralix is dying before its place is taken up by other species. To investigate the causes, we used both old and new data. Results showed that presence of Molinia caerulea and Calluna vulgaris were substantial in the former E. tetralix dominated areas. Measurements of the C/N ratio in the morlayer were between 21 and 26 under the E. tetralix stands. As the expected C/N ratio in a healthy nutrient poor ecosystem like the E. tetralix wet heathland is around 30, this indicates that the ratio is probably decreasing and, correspondingly, the probability of nitrogen leaching from the ecosystem is increasing. The morlayer pH was extremely low—between 3.03 and 3.78. This represents a pH decline since the 1960s, where pH values generally were above 4. This supports the hypothesis that the decrease in morlayer pH is the major factor explaining the disappearance of E. tetralix and that measures to increase pH should be considered as part of the recommendations for relevant future management.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-012-0251-z) contains supplementary material, which is available to authorized users.     

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.     

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.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.