Airborne trace element pollution in 11 European cities assessed by exposure of standardised ryegrass cultures

Within a European biomonitoring programme, Italian ryegrass (Lolium multiflorum Lam.) was employed as accumulative bioindicator of airborne trace elements (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, V, Zn) in urban agglomerations. Applying a highly standardised method, grass cultures were exposed for consecutive periods of four weeks each to ambient air at up to 100 sites in 11 cities during 2000–2002. Results of the 2001 exposure experiments revealed a clear differentiation of trace element pollution within and among local monitoring networks. Pollution was influenced particularly by traffic emissions. Especially Sb, Pb, Cr, Fe, and Cu exhibited a very uneven distribution within the municipal areas with strong accumulation in plants from traffic-exposed sites in the city centres and close to major roads, and moderate to low levels in plants exposed at suburban or rural sites. Accumulation of Ni and V was influenced by other emission sources. The biomonitoring sites located in Spanish city centres featured a much higher pollution load by trace elements than those in other cities of the network, confirming previously reported findings obtained by chemical analyses of dust deposition and aerosols. At some heavily-trafficked sites, legal thresholds for Cu, Pb, and V contents in foodstuff and animal feed were reached or even surpassed. The study confirmed that the standardised grass exposure is a useful and reliable tool to monitor and to assess environmental levels of potentially toxic compounds of particulate matter.     

Regional NOx emission inversion through a four-dimensional variational approach using SCIAMACHY tropospheric NO2 column observations

In this paper, the NOx emission scaling factors applied over the 2001 National Emissions Inventory (NEI) are estimated through a four-dimensional variational (4D-Var) approach using SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY) tropospheric NO₂ columns measured during summer 2004. In the “top-down” approach, two-month average NO₂ columns are assimilated into a regional chemical transport model (CTM), STEM, using different assimilation setups. In a basic setup, NOx emissions are adjusted by assimilating the NO₂ columns. A more general setup of emission inversion allows the initial O₃ concentrations be adjusted along with the NOx emissions. A final case is set up to assimilate both the NO₂ columns and O₃ measurement from various platforms while allowing adjustments of both the NOx emissions and the initial O₃ concentrations. It is found that the addition of O₃ measurements did not improve the NOx emission inversion. With the NOx emission at surface and upper levels being adjusted separately, results from four cases show that the elevated NOx emission reduction ranges from 8.9% to 11.4%, and the surface NOx emission reduction is up to 6.6%. All the cases show NOx emission reduction in Ohio valley and Washington, District of Columbia areas.     

Radon-222 exhalation from open ground on and around a uranium mine in the wet-dry tropics

Radon-222 exhalation from the ground surface depends upon a number of variables such as the 226Ra activity concentration and its distribution in soil grains; soil grain size; soil porosity, temperature and moisture; atmospheric pressure, rainfall and temperature. In this study, 222Rn exhalation flux density measurements within and around the Ranger uranium mine in northern Australia were performed to investigate the effect of these variables within a tropical region. Measurements were taken at the waste rock dumps, ore stockpiles, mine pits, and at sites where effluent water with elevated 226Ra concentration has been spray irrigated over land, as well as at sites outside the mine. The sites selected represented a variety of geomorphic regions ranging from uranium-bearing rocks to ambient soils. Generally, wet season rains reduced 222Rn exhalation but at a few sites the onset of rains caused a step rise in exhalation flux densities. The results show that parameters such as 226Ra activity concentration, soil grain size and soil porosity have a marked effect on 222Rn flux densities. For similar geomorphic sites, 226Ra activity concentration is a dominant factor, but soil grain size and porosity also influence 222Rn exhalation. Surfaces with vegetation showed higher exhalation flux densities than their barren counterparts, perhaps because the associated root structure increases soil porosity and moisture retention. Repeated measurements over one year at eight sites enabled an analysis of precipitation and soil moisture effects on 222Rn exhalation. Soil moisture depth profiles varied both between seasons and at different times during the wet season, indicating that factors such as duration, intensity and time between precipitation events can influence 222Rn flux densities considerably.     

Aryl hydrocarbon receptor-mediated activity of atmospheric particulate matter from an urban and a rural site in Switzerland

Atmospheric particulate matter (PM) is an air-suspended mixture of solid and liquid particles that vary in size, shape, and chemical composition. Long-term exposure to elevated concentrations of fine atmospheric particles is considered to pose a health threat to humans and animals. In this context, it has been hypothesized that toxic chemicals such as polycyclic aromatic hydrocarbons (PAHs) play an important role. Some PAHs are known to be carcinogenic and it has been shown that carcinogenic effects of PAHs are mediated by the aryl hydrocarbon receptor (AhR). In this study, PM1 was collected at a rural and an urban traffic site during an intense winter smog period, in which concentration of PM1 often exceeded 50 μg m^?3. We applied an in vitro reporter gene assay (DR-CALUX) to detect and quantify PM1-associated chemicals that induce AhR-mediated gene expression. This activity was expressed as CALUX equivalents of 2,3,7,8-tetrachlorodibenzodioxin (PM-TCDD-CEQs). In addition, concentrations of PAHs in the PM1 extracts were determined using gas chromatography/high-resolution mass spectrometry. Concentrations of PM-TCDD-CEQs ranged from 10 to 85 pg m^?3 and from 19 to 87 pg m^?3 at the urban and rural site, respectively. By the use of known relative potency factors, the measured concentration of a PAH was converted into a PAH-TCDD-CEQ concentration. ΣPAH-TCDD-CEQ and PM-TCDD-CEQ were highly correlated at both sites (r² = 0.90 and 0.69). The calculated ΣPAH-TCDD-CEQs explain between 2% and 20% of the measured PM-TCDD-CEQs. Benzo[k]fluoranthene was the most important PAH causing approximately 60% of the total ΣPAH-TCDD-CEQ activity. In contrast to NO, CO, PM10, and PM1, the concentration of PM-TCDD-CEQs showed no significant difference between the two sites. No indications were found that road traffic emissions caused elevated concentrations of PM-TCDD-CEQs at the urban traffic site.     

Long-term (≥20 years) application of fertilizers and straw return enhances soil carbon storage: a meta-analysis

Increasing soil carbon (C) storage is crucial to addressing climate change and ensuring food security. The C sequestration potential of the world’s cropland soil is 0.4–0.8 Pg soil C year^?1, which may be achieved through the adoption of recommended management practices (RMPs), including fertilizer management. This study aimed to quantitatively evaluate the influence of long-term application of different fertilizers and straw retention on soil organic carbon (SOC) storage, to compare the calculated response ratios with Intergovernmental Panel on Climate Change (IPCC)-recommended default relative stock change factors, and to propose recommendations for enhancing SOC sequestration. The meta-analysis indicated that the long-term application of chemical fertilizers (CF), organic fertilizers (OF), combined chemical and organic fertilizers (CFOF), and straw return (SR) significantly enhanced the SOC storage. Response ratios varied significantly (p < 0.05) across different fertilization measures and climatic zones, and was sensitive to the initial SOC content. The mean response ratio was 0.94 for no fertilizer (NF), 1.08 for CF, 1.48 for OF, 1.38 for CFOF, and 1.28 for SR. When IPCC default values for response ratios were applied, SOC storage with OF and CFOF treatments in warm temperate regions with a dry climate was underestimated by 26%, and in the cool temperate region with a moist climate was overestimated by 25% (p < 0.05). Analysis showed that sustained application of organic fertilizers and straw return could be a beneficial measures to mitigate climate change and ensure food security in China. Our findings highlight the importance of deriving SOC stock change factors for a detailed classification of cropland by fertilizer management, climate, and soil types in order to more accurately reflect the effects of policy measures.     

Carbon flows and carbon use in the German anthroposphere: An inventory

Today, global climate change is one of the most urgent environmental problems. The atmospheric concentration of carbon dioxide (CO₂) has to be stabilised by significant reductions of CO₂ emissions in the next decades to keep the expected temperature rise within tolerable borders. Efforts exceeding the implemented measures to reduce CO₂ emissions in Germany are desirable. An important pre-condition for such measures is a scientific-based inventory of the sources, sinks, and use of carbon.In this paper, we present CarboMoG, i.e. Carbon Flow Model of Germany. CarboMoG is a carbon flow model covering carbon flows, carbon sources and sinks in Germany and the German anthroposphere, showing concurrent energy and non-energy use of carbon sources.The model consists of seven modules in German anthroposphere following the German classification of economic sectors. Carbon flows to and from atmosphere and lithosphere as well as imports and exports were included into the model. The model comprises roughly 220 material flows determined based on material flow procedures for the base year 2000.Main sources of carbon are fossil energy carriers from lithosphere and uptake of CO₂ by crops (52% resp. 48% of all carbon sources). The model calculations show that import of energy carriers dominates total carbon import to Germany (82%). Total non-energy use of carbon in Germany is significantly higher than energy use (386 Mt C and 230 Mt C, resp.). Carbon throughput of Industry is greatest (about 224 Mt C input), followed by Energy (about 129 Mt C input). Agriculture and Forestry & Industry show the highest figure for non-energy use of carbon, energy use of carbon is largest in the Energy sector. Emissions of CO₂ to atmosphere account for 94% of all carbon flows to sinks in Germany. Carbon accumulates in German anthroposphere 5 Mt C in 2000.     

Chelate assisted phytoextraction of heavy metals from soil. Effect, mechanism, toxicity, and fate of chelating agents

The low-cost, plant-based phytoextraction technique has often been described as a promising technique to remediate heavy metal contaminated agricultural land. The application of chelating agents has shown positive effects in increasing the solubility of heavy metals in soil and therefore in enhancing phytoextraction. This paper gives an overview of the chelating agents applied in recent studies. Various synthetic aminopolycarboxylic acids, such as ethylene diamine tetraacetic acid, and natural ones such as, ethylene diamine disuccinate and nitrilotriacetic acid, are described. Additionally, results of the application of natural low molecular weight organic acids, such as citric and tartaric acid are given. The effectiveness of these different chelating agents varies according to the plant and the heavy metals used. Furthermore, a focus is laid on the chelating agents fate after application and on its toxicity to plants and soil microorganisms, as well as it degradation. The rate of degradation is of great importance for the future of chelate assisted phytoextraction as it has a direct impact on the leaching probability. An effective prevention of leaching will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction, but a satisfactory solution to this key issue has so far not been found. Possibly further experiments in the field of enhanced phytoextraction will be able to solve this major problem, but over decades various greenhouse experiments and recently field experiments have resulted in different observations. Therefore, it is questionable if further research in this direction will lead to a promising solution. Phytoextraction has possibly reached a turning point in which it should distance itself from chelate assisted phytoextraction and focus on alternative options.     

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 microg l(-1) as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t1/2) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t1/2 values could not be determined for MBT and TPhT (t1/2>18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively.     

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH^?, BBr₃, RuO₄, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.