A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS, with limits of detection of 0.3 ng m⁻³), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD-GC-MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of 1 μg m⁻³ was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s⁻¹) and 292 nm excitation. A novel method for rapid analysis of atmospheric PAHs by laser induced fluorescence allows for more detailed trend determinations.

In this study, a biomonitoring project using the moss Scorpiurum circinatum was carried out to evaluate the deposition and biological effects of heavy metals in the area of Acerra (Naples, S Italy), one of the vertices of the sadly called "Italian triangle of death" owing to the dramatic increase in tumours. The results clearly indicated that the study area is heavily polluted by heavy metals, a large proportion of which is likely present in the atmosphere in particulate form. The ultrastructural organization of exposed samples was essentially preserved, but cell membrane pits, cytoplasm vesicles and concentric multilamellar/multivesicular bodies, probably induced by pollution, were found, which may be involved in the tolerance mechanisms to metal pollution in this moss species. Although severe biological effects were not found at the ultrastructural level in the exposed moss, effects on humans, especially after long-term exposure, are to be expected. The moss Scorpiurum circinatum indicates that the "Italian triangle of death" is heavily polluted by heavy metals.

In forest soils along vertical profiles located in different parts of the Alps, concentrations of persistent organic pollutants (POPs), namely organochlorine pesticides (OCPs) like dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), heptachlor, aldrin, dieldrin and mirex, were measured. Though local characteristics of the sites are influenced by numerous factors like orographic and meteorological parameters, forest stand characteristics and humus parameters, we ascertained a marked vertical increase of concentrations of some organochlorine compounds in the soil. On the basis of climatological values of each site, we found that the contamination increase with altitude can be ascribed to a certain ‘cold condensation effect’. In addition, the perennial atmospheric deposition of POPs is controlled by precipitation. Other key parameters explaining the accumulation of POPs are the soil organic carbon stocks, the turnover times, the re-volatilisation and degradation processes, which vary with altitude. Caused by temperature-dependent processes regarding deposition, re-volatilization and decomposition of POPs, the concentration of organochlorine pesticides varies in the Alpine region with altitude.

The Tibetan Plateau (TP) is an ideal place for monitoring the atmospheric environment of low to mid latitudes. In total 54 soil samples from the western TP were analyzed for major and trace elements. Results indicate that concentrations of some typical "pollution" elements (such as As) are naturally high here, which may cause incorrect evaluation for the source region of these elements, especially when upper continental crust values are used to calculate enrichment factors. Because only particles <20 μm are transportable as long distances, elemental concentrations of this fraction of the TP soils are more reliable for the future aerosol related studies over the TP. In addition, REE compositions of the TP soils are unusual, highly characteristic and can be used as an effective index for identifying dust aerosol from the TP. High concentrations of some elements of the Tibetan soils can cause incorrect evaluation for the source region of these elements during aerosol related study.

On Zugspitze (2670 m a.s.l.), Alps, higher concentrations were observed during a winter than during a summer measurement campaign of PAHs, chlorobenzenes (43.6 vs. 2.0 pg m−3) and DDTs (3.7 vs. 1.2 pg m−3), while hexachlorocyclohexanes and PCBs were found at similar levels. The PCB, HCH and DDT levels are among the lowest ever reported from outside the Arctic. Mostly lower levels were found in samples collected in summer than in winter despite a significant boundary layer air influence, but no such influence on samples collected during the winter campaign. Boundary layer influence was quantified by Lagrangian particle dispersion model retroplume analyses. Photochemical lifetimes corresponding to kOH < 1.5 × 10−12 cm3 molec−1 s−1 are found for p,p′-DDT, kOH < 0.75 × 10−12 cm3 molec−1 s−1 for p,p′-DDE and kOH < 1.0 × 10−12 cm3 molec−1 s−1 for p,p′-DDD. Persistent organic pollutants have been observed at a mountain site in the Alps showing that very low concentrations can be found in the free troposphere.

As part of the Rain In Cumulus over the Ocean Experiment (RICO) and the Puerto Rico Aerosol and Cloud Study (PRACS), cloud water was collected at East Peak (EP) in Puerto Rico. The main objective of this study was to determine the concentrations of water-soluble species (Cl⁻, NO₃ ⁻, SO₄ ²⁻, NH₄ ⁺, Ca²⁺, H⁺, Mg²⁺, K⁺, and Na⁺) in water samples taken from clouds influenced by tropical trade winds. The most abundant inorganic species were Na⁺ (average 465 μeq l⁻¹) and Cl⁻ (434 μeq l⁻¹), followed by Mg²⁺ (105 μeq l⁻¹), SO₄ ²⁻ (61 μeq l⁻¹), and NO₃ ⁻ (25 μeq l⁻¹). High concentrations of nss-SO₄ ² (28 μeq l⁻¹), NO₃ ⁻ (86 μeq l⁻¹), and H⁺ (14.5 μeq l⁻¹) were measured with a shift in air masses origin from the North Atlantic to North American continent, which reflected a strong anthropogenic influence on cloud chemistry at EP. Long-range transport of particles and acid gases seems to be the factor responsible for fluctuations in concentrations and pH of cloud water at East Peak. When under trade wind influences the liquid phase concentrations of all inorganic substances were similar to those found in clouds in other clean maritime environments.

PM2.5 and PM10 samples were collected in the urban atmosphere of Elche (southeastern Spain) between December 2004 and November 2005. The samples were analyzed for mass and water-soluble inorganic ions (Na⁺, [graphic removed] , K⁺, Ca²⁺, Mg²⁺, Cl⁻, [graphic removed] and [graphic removed] ) with the aim of investigating the influence of the climatic and geographic features of a coastal semiarid area on the contribution of these species to PM levels. Secondary inorganic ions ( [graphic removed] , [graphic removed] , [graphic removed] ) were the major components in the fine fraction (PM2.5), accounting for 40% of the total mass. The relationship between non-marine [graphic removed] and [graphic removed] indicated that fine sulfate particles were completely neutralized by ammonium. In the coarse fraction (PM10-2.5), nitrate (as NaNO₃ and Ca(NO₃)₂), together with crustal (CaCO₃) and marine species (NaCl) accounted for almost 50% of the total mass. Fine sulfate and coarse nitrate showed summer maximums. In contrast, the concentrations of fine [graphic removed] were lowest in the warm period. Ammonium presented both winter and summer maximums. The levels of marine ions, except for coarse Cl⁻, were highest in summer when the dominant wind flow is from the sea. No significant seasonal variations were observed for coarse Ca²⁺ and [graphic removed] . The concentrations of all inorganic ions increased during Saharan dust events, in particular, fine [graphic removed] and [graphic removed] and coarse [graphic removed] . Coarse calcium was proved not to be a good tracer for this type of episode in our region since the average levels of this cation are elevated and the relative increase in its concentrations during African events was not as high as expected.

Background, aim, and scope Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2',3,3',5,5',6,6'-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment.

Background, aim, and scope The Arctic holds large stores of minerals, and extracted materials are provided to the world's economy; in this sense, the Arctic issue associated with mining is not local but global. In a part of the Arctic region (the Kola Peninsula, 66-70° N and 28-41° E), metal levels are generally elevated in the lake sediment. There is a question as to what results in elevated metal levels--a natural process (naturally abundant minerals) or an anthropogenic process (mining and metallurgy). In terms of solving this question, Staroe lake located on the Kola Peninsula was researched as a case study. Materials and methods The following parameters were determined in relation with Staroe lake: (1) the current quality of the lake's water--each 1,000-ml sample was collected at a surface point and a deep point (near the bottom layer), and the collected samples were directly analyzed after filtration; (2) atmospheric bulk deposition--bulk deposition was collected using a set of three rainwater samplers near the lake. In addition, bulk deposition was collected in a background site (250 km to the southwest of the smelter complex) as a reference; and (3) sediment profile (plus principal component analysis)--lake-bottom sediment was collected by an open-gravimetric column sampler equipped with an automatic diaphragm. After collection, the sample columns were cut at a 1-cm interval for analysis. Eigenvalues and variances by factor were calculated from the correlation coefficients. Results The obtained data show that (1) naturally poor elements (Cu, Ni, Si, and SO₄ ²⁻) dominantly influence the lake's water quality; (2) they are transported from the anthropogenic sources to the study lake through the atmospheric pathway; (3) mainly the contents of Cu, Ni, Sr, and Ca have influenced the sediment quality since the 1950s, corresponding to the industrial movement; and (4) Cu, Ni, and Sr originate from an anthropogenic source (smelter), and Ca originates from both natural and anthropogenic sources. Discussion As compared with the Russian standard (San Pin 2.1.980-00), the contents of NO₃ ⁻ (50.3 ± 0.1 mg l⁻¹) and particulates (2.3 ± 0.2 mg l⁻¹) exceeded the standard levels (0.7 mg l⁻¹ NO₃ ⁻ and 45 mg l⁻¹ particulates); Staroe lake may be slightly contaminated. However, the contamination factor (comparison with the background data) implies that Staroe lake is considerably contaminated. There is a strong possibility that fine overburden detritus (<0.1 mm diameter) may be transported from an open pit to the study lake by natural forces such as wind. Although it is difficult to suppose that one factor dominantly affects the sediment quality, it follows from a factor analysis that factors 1 and 2 account for about 70% of the total variance: Factor 1 is the most dominant, and factor 2 is the second most dominant in the variability of sediment quality. It is considered that Cu, Sr, and Ni in factor 1 originate from anthropogenic sources because they are poor in sediment rocks. Conclusions The field survey conducted in Staroe lake can give the following answers to the key objectives: (1) The present water quality is affected by Cu, Ni, Si, and SO₄ ²⁻ in light of the contamination factor, and these elements originate from anthropogenic sources (the smelter and the open pit) and are transported to the lake through the atmospheric pathway; (2) the sediment profile and statistic analysis show that the lake quality has been influenced by deposition of metals since the 1950s; and (3) Cu, Ni, Sr, and Ca have influenced the sediment quality in light of the most dominant factor--Cu, Ni, and Sr originate from an anthropogenic source, whereas Ca comes from both natural and anthropogenic sources. Recommendations and perspectives The presented lake survey shows that the dispersion of human-related pollutants via the atmospheric pathway takes place in the Arctic region. If the current pollution continues without countermeasures, the high-latitude environment may lose its original characteristics; hence, this subject is important when considering how to implement a wide range of environmental protection measures in the Arctic.

Background, aims, and scope Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment's areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4-95 in lipid of planktovores and 7-150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21-31 in Themisto libellula (chatka), 26-42 in Boreocadus saida (Polar cod), and 5-27 in Gadus morhua (cod) liver. Discussion The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment's environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area.