The remoteness and low population in the Arctic allow us to study global environmental processes, where the analysis of indicators can provide useful information about local and distant pollution sources. Fresh snow represents a convenient indicator of regional and transboundary atmospheric contamination sources, entrapping aerosols, and particulates like a natural autosampler of the environment. Lead stable isotopes are widely used to trace and monitor local and distant pollution sources. However, the behavior of Pb within different snow components is still not thoroughly studied, and its significance could be underestimated if only larger particulates are accounted for. We collected snow and samples from potential sources (fuel, rocks, coal) in three Arctic localities: Nuuk (Greenland), Reykjavik (Iceland), and Longyearbyen (Svalbard). We separated the filtrate from the filter residue through 0.45 μm nitrocellulose membranes to isolate the low-diameter particles associated with long-range transport from larger particles of mostly local natural origin. Filtrates yielded higher EFs (enrichment factor as the Pb/Al ratio relative to the upper crust) than filtration residues (80 ± 104 and 2.1 ± 1.1, respectively), and Pb isotope signals similar to fuel and coal (206Pb/207Pb are 1.199 ± 0.028 in coal, 1.168 ± 0.029 in filtrates, 1.163 ± 0.013 in fuel, 1.137 ± 0.045 in residues, and 0.985 ± 0.020 in rocks). In contrast to filtrates, the filter residues present wider ranges of Pb isotope compositions and crustal contributions and lower EFs, so we suggest that filtrate contains Pb from fuel combustion more selectively, while the residue carries a more considerable contribution of local mineral dust that can mask the contribution of other anthropogenic or distant natural sources. These findings add weight to the notion that filtrates are a more selective measure of metal deposition from long-range anthropogenic emissions compared to analyzing bulk melted snow or only filter residues.
After the phasing out of leaded gasoline, Pb emissions to the atmosphere dramatically decreased, and other sources became more significant. The contribution of unleaded gasoline has not been sufficiently recognized; therefore, we evaluated the impact of Pb from unleaded gasoline in a relatively pristine area in Subarctic NE Norway. The influence of different endmembers (Ni slag and concentrate from the Nikel smelter in Russia, PM10filters, and traffic) on the overall Pb emissions was determined using various environmental samples (snow, lichens, and topsoils) and Pb isotope tracing. We found a strong relationship between Pb in snow and the Ni smelter. However, lichen samples and most of the topsoils were contaminated by Pb originating from the current use of unleaded gasoline originating from Russia. Historical leaded and recent unleaded gasoline are fully distinguishable using Pb isotopes, as unleaded gasoline is characterized by a low radiogenic composition (206Pb/207Pb = 1.098 and208Pb/206Pb = 2.060) and remains an unneglectable source of Pb in the region.
- MeSH
- atmosféra chemie MeSH
- benzin analýza MeSH
- izotopy analýza MeSH
- látky znečišťující životní prostředí analýza MeSH
- lišejníky chemie MeSH
- monitorování životního prostředí * MeSH
- olovo analýza MeSH
- sníh chemie MeSH
- výfukové emise vozidel analýza MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Norsko MeSH
- Rusko MeSH
Samples of lichens, snow and particulate matter (PM10, 24 h) are used for the source identification of air pollution in the heavily industrialized region of Ostrava, Upper Silesia, Czech Republic. An integrated approach that uses different environmental samples for metal concentration and Pb isotope analyses was applied. The broad range of isotope ratios in the samples indicates a combination of different pollution sources, the strongest among them being the metallurgical industry, bituminous coal combustion and traffic. Snow samples are proven as the most relevant indicator for tracing metal(loid)s and recent local contamination in the atmosphere. Lichens can be successfully used as tracers of the long-term activity of local and remote sources of contamination. The combination of PM10 with snow can provide very useful information for evaluation of current pollution sources.
- MeSH
- atmosféra chemie MeSH
- izotopy analýza MeSH
- kovy analýza MeSH
- látky znečišťující vzduch analýza MeSH
- lišejníky metabolismus MeSH
- monitorování životního prostředí metody MeSH
- pevné částice analýza MeSH
- průmysl MeSH
- sníh chemie MeSH
- uhlí analýza MeSH
- znečištění ovzduší analýza MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ(65)Cu and δ(66)Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ(65)Cu and δ(66)Zn values in snow and rime, extracted by diluted HNO3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ(65)Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ(65)Cu value of pollution sources (-1.17‰). The variability in δ(65)Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ(66)Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ(66)Zn value of pollution sources (-0.23‰). The variability in δ(66)Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe.
There is strong evidence for a shifting of range boundaries by many temperate butterfly species to higher altitudes and latitudes. Climate change represents a potential threat to mountain fauna. Nevertheless, information on ecophysiological limits of individual species is scarce. We studied the lower thermal limits of four species representing the prevailingly mountain Holarctic butterfly genus Erebia. We measured the cold tolerance of hibernating larvae, namely the supercooling point (SCP) and the lower lethal temperature (LLT). Three mountain species were freeze avoiding, with various levels of SCP (-8 to -22 degree C), and LLT close to SCP. The only exception was lowland E. medusa, whose caterpillars were freeze tolerant with LLT (-21 degree C) slightly below its SCP (-17 degree C). Surprisingly, LLT was highest in the alpine E. tyndarus and lowest in E. medusa inhabiting lower altitudes with higher mean winter temperatures. We explain the observed reversed altitudinal cline in cold hardiness by the buffering function of snow cover in the hibernacula of caterpillars that is strong at high mountains but irregular, unpredictable and thus unreliable in lowlands.
- MeSH
- aklimatizace * MeSH
- hibernace MeSH
- klimatické změny MeSH
- larva fyziologie MeSH
- motýli fyziologie MeSH
- nízká teplota MeSH
- sníh chemie MeSH
- zvířata MeSH
- Check Tag
- ženské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
We measured the kinetics of ozonation reaction of 1,1-diphenylethylene (DPE) in artificial snow, produced by shock freezing of DPE aqueous solutions sprayed into liquid nitrogen. It was demonstrated that most of the reactant molecules are in direct (productive) contact with gaseous ozone, thus the technique produces snow with organic molecules largely ejected to the surface of snow grains. The kinetic data were used to evaluate the snow specific surface area (∼70 cm(2) g(-1)). This number is a measure of the availability of the molecules on the surface for chemical reaction with gaseous species. The experimental results were consistent with the Langmuir-Hinshelwood type reaction mechanism. DPE represents environmentally relevant compounds such as alkenes which can react with atmospheric ozone, and are relatively abundant in natural snow. For typical atmospheric ozone concentrations in polar areas (20 ppbv), we estimated that half-life of DPE on the surface of snow grains is ∼5 days at submonolayer coverages and -15 °C.
- MeSH
- molekulární struktura MeSH
- ozon chemie MeSH
- sníh chemie MeSH
- styreny chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The utilization of artificial snow for environmentally relevant (photo)chemical studies was systematically investigated. Contaminated snow samples were prepared by various methods: by shock freezing of the aqueous solutions sprayed into liquid nitrogen or inside a large walk-in cold chamber at -35 °C, or by adsorption of gaseous contaminants on the surface of artificially prepared pure or natural urban snow. The specific surface area of artificial snow grains produced in liquid nitrogen was determined using valerophenone photochemistry (400-440 cm(2) g(-1)) to estimate the surface coverage by small hydrophobic organic contaminants. The dynamics of recombination/dissociation (cage effect) of benzyl radical pairs, photochemically produced from 4-methyldibenzyl ketone on the snow surface, was investigated. The initial ketone loading, c = 10(-6)-10(-8) mol kg(-1), only about 1-2 orders of magnitude higher than the contaminant concentrations commonly found in nature, was already well below monolayer coverage. We found that the efficiency of out-of-cage reactions decreased at much higher temperatures than those previously determined for frozen solutions; however, the cage effect was essentially the same no matter what technique of snow production or ketone deposition/uptake was used, including the experiments with collected natural snow. The experimental observation that the contaminant molecules are initially self-associated even at the lowest concentrations was supported by DFT calculations. We conclude that, contrary to frozen aqueous solutions, in which the impurities reside in a 3D cage (micropocket), contaminant molecules located on the artificial snow grain surface at low concentrations can be visualized in terms of a 2D cage. Artificial snow thus represents a readily available study matrix that can be used to emulate the natural chemical processes of trace contaminants occurring in natural snow.
- MeSH
- adsorpce MeSH
- chemické modely MeSH
- fotochemické procesy MeSH
- ketony analýza chemie MeSH
- látky znečišťující vzduch analýza chemie MeSH
- monitorování životního prostředí metody MeSH
- povrchové vlastnosti MeSH
- sníh chemie MeSH
- teplota MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Basic operation principles of a lightweight, low power, low cost, portable ion chromatograph utilizing open tubular ion chromatography in capillary columns coated with multi-layer polymeric stationary phases are demonstrated. A minimalistic configuration of a portable IC instrument was developed that does not require any chromatographic eluent delivery system, nor sample injection device as it uses gravity-based eluent flow and hydrodynamic sample injection adopted from capillary electrophoresis. As a detection device, an inexpensive commercially available capacitance sensor is used that has been shown to be a suitable substitute for contactless conductivity detection in capillary separation systems. The built-in temperature sensor allows for baseline drift correction typically encountered in conductivity/capacitance measurements without thermostating device. The whole instrument does not require any power supply for its operation, except the detection and data acquisition part that is provided by a USB port of a Netbook computer. It is extremely lightweight, its total weight including the Netbook computer is less than 2.5kg and it can be continuously operated for more than 8h. Several parameters of the instrument, such as detection cell design, eluent delivery systems and data treatment were optimized as well as the composition of eluent for non-suppressed ion chromatographic analysis of common inorganic cations (Na(+), NH(4)(+), K(+), Cs(+), Ca(2+), Mg(2+), transition metals). Low conductivity eluents based on weakly complexing organic acids such as tartaric, oxalic or pyridine-2,6-dicarboxylic acids were used with contactless capacitance detection for simultaneous separation of mono- and divalent cations. Separation of Na(+) and NH(4)(+) cations was optimized by addition of 18-crown-6 to the eluent. The best separation of 6 metal cations commonly present in various environmental samples was accomplished in less than 30min using a 1.75mM pyridine-2,6-dicarboxylic acid and 3mM 18-crown-6 eluent with excellent repeatability (below 2%) and detection limits in the low micromolar range. The analysis of field samples is demonstrated; the concentrations of common inorganic cations in river water, mineral water and snow samples were determined.
- MeSH
- chemické znečištění vody analýza MeSH
- chemický průmysl MeSH
- hexachlorbenzen analýza MeSH
- látky znečišťující vodu analýza MeSH
- látky znečišťující vzduch analýza MeSH
- mateřské mléko chemie MeSH
- rezidua pesticidů analýza MeSH
- roční období MeSH
- sníh chemie MeSH
- voda chemie MeSH
- vzduch analýza MeSH
- znečištění ovzduší MeSH
