Pavel Čupr

Mobility, bioavailability, and toxic effects of cadmium in soil samples

Total concentration is not a reliable indicator of metal mobility or bioavailability in soils. The physicochemical form determines the behavior of metals in soils and hence the toxicity toward terrestrial biota. The main objectives of this study were the application and comparison of three approaches for the evaluation of cadmium behavior in soil samples. The mobility and bioavailability of cadmium in five selected soil samples were evaluated using equilibrium speciation (Windermere humic aqueous model (WHAM)), extraction procedures (Milli-Q water, DMSO, and DTPA), and a number of bioassays (Microtox, growth inhibition test, contact toxicity test, and respiration). The mobility, represented by the water-extractable fraction, corresponded well with the amount of cadmium in the soil solution, calculated using the WHAM (r(2)=0.96, P<0.001). The results of the ecotoxicological evaluation, which represent the bioavailable fraction of cadmium, correlated well with DTPA extractability and also with the concentration of free cadmium ion, which is recognized as the most bioavailable metal form. The results of the WHAM as well as the results of extraction experiments showed a strong binding of cadmium to organic matter and a weak sorption of cadmium to clay minerals.

Soil burdens of persistent organic pollutants - their levels, fate and risk. Part I. Variation of concentration ranges according to different soil uses and locations.

Detailed soil screening data from the Czech Republic as a typical Central European country are presented here. Determination of a wide selection of organic and inorganic pollutants as well as an assessment of specific soil parameters allowed us to study the soil contamination in relation to the land use and soil properties. While HCHs and HCB were found at highest levels in arable soils, the higher concentrations of PCDDs/Fs, PCBs, PAHs and DDTs were observed in high altitude forest soils. Concentrations of these compounds strongly correlated with the soil organic carbon content. Several possible reasons have been suggested for the observed higher concentrations in mountain forest soils but the impact of each of these influencing factors remains to be identified. An inventory of the soil contamination is needed as a first step in our effort to estimate an extent to which the secondary sources contribute to the enhanced atmospheric levels of POPs.

Uptake of polychlorinated biphenyls and organochlorine pesticides from soil and air into radishes (Raphanus sativus)

Uptake of organochlorine pesticides and polychlorinated biphenyls from soil and air into radishes was measured at a heavily contaminated field site. The highest contaminant concentrations were found for DDT and its metabolites, and for beta-hexachlorocyclohexane. Bioconcentration factor (BCF, defined as a ratio between the contaminant concentration in the plant tissue and concentration in soil) was determined for roots, edible bulbs and shoots. Root BCF values were constant and not correlated to log K(OW). A negative correlation between BCF and log K(OW) was found for edible bulbs. Shoot BCF values were rather constant and varied between 0.01 and 0.22. Resuspended soil particles may facilitate the transport of chemicals from soil to shoots. Elevated POP concentrations found in shoots of radishes grown in the control plot support the hypothesis that the uptake from air was more significant for shoots than the one from soil. The uptake of POPs from air was within the range of theoretical values predicted from log K(OA).

Can pine needles indicate trends in the air pollution levels at remote sites

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V(EQ)) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.

Environment and human exposure to persistent organic pollutants (POPs) in India: a systematic review of recent and historical data.

Persistent organic pollutants (POPs) have been used in a wide range of agricultural and industrial commodities, resulting in vigorous deterioration of environment and human health. A number of studies on the occurrence of POPs confirm their presence in various environmental compartments and human body. In order to deal with this global concern, India has recently prepared the National Implementation Plan (NIP) of the Stockholm Convention. Common beliefs point at India as a hot spot of POP contamination and human exposure; however no systematic analysis was ever performed so far considering all available past data on POP occurrence. This review aims to examine the distribution pattern of POPs in multicompartment environment and human samples, meta-analysis of time trends in exposure levels to environment and humans, and cross country comparison of POP contamination with China. Based on this review, it can be concluded that the Indian environment and human population are highly contaminated by DDTs and HCHs; however scarcity of data on other POPs makes it challenging to assess their nationwide human and environmental exposure. No evidence of a general decline in DDT and HCH residues in the environment and human body come out from the meta-analysis of time trend. While comparing contamination levels between India and China, tendency towards decline in POP contamination is visible in China, unlike India.

Photochemical activity of organic compounds in ice induced by sunlight irradiation: The Svalbard project

Field experiments in Ny-Alesund, Spitsbergen Island (Svalbard) demonstrated that water ice can be a suitable reaction medium for photochemical transformations of organic pollutants. Several aromatic carbonyl, chloro, nitro or hydroxy compounds, frozen in the ice-matrix samples, underwent very efficient sunlight-induced chemical changes. The photoproducts, in many cases completely different from those obtained from liquid solution photolysis, might pose a high toxicological risk to biota when they enter the environment. It is concluded that the results could be applicable to natural snow and ice, and that possible photochemical transformations should be considered in the ice-core record studies.

Soil burdens of persistent organic pollutants--their levels, fate and risks Part III. Quantification of the soil burdens and related health risks in the Czech Republic.

A total number of 471 soil samples collected during the period of 1996-2006 from the agricultural and forest areas of the Czech Republic were analyzed for their content of persistent organic pollutants (POPs). Spatial variability of the POP concentrations was assessed using an IDW spatial GIS model analysis. For every grid of the network, resulting modeled levels of contamination allowed for estimation of the total burden of POPs in soils. Potential risks associated with contaminated soils were assessed as well. Database of the old ecological burdens counting 3061 sampling sites was used to adjust the model and incorporate the risks of heavily contaminated sites. The high levels of health risks were only found at less than 1% of the area of interest. The IDW modeling proved to be a useful tool for screening of the health risks in the large areas with scarce monitoring data. Presented approach can be applied in the risk management, to support an efficient targeting of the risk reduction measures, or to improve a design of the national monitoring.

Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport

This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 μm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs.

Mineralogical, chemical and toxicological characterization of urban air particles

Systematic characterization of morphological, mineralogical, chemical and toxicological properties of various size fractions of the atmospheric particulate matter was a main focus of this study together with an assessment of the human health risks they pose. Even though near-ground atmospheric aerosols have been a subject of intensive research in recent years, data integrating chemical composition of particles and health risks are still scarce and the particle size aspect has not been properly addressed yet. Filling this gap, however, is necessary for reliable risk assessment. A high volume ambient air sampler equipped with a multi-stage cascade impactor was used for size specific particle collection, and all 6 fractions were a subject of detailed characterization of chemical (PAHs) and mineralogical composition of the particles, their mass size distribution and genotoxic potential of organic extracts. Finally, the risk level for inhalation exposure associated to the carcinogenic character of the studied PAHs has been assessed. The finest fraction (<0.45 μm) exhibited the highest mass, highest active surface, highest amount of associated PAHs and also highest direct and indirect genotoxic potentials in our model air sample. Risk assessment of inhalation scenario indicates the significant cancer risk values in PM 1.5 size fraction. This presented new approach proved to be a useful tool for human health risk assessment in the areas with significant levels of air dust concentration.

Which compounds contribute most to elevated airborne exposure and corresponding health risks in the Western Balkans

A majority of ongoing monitoring of persistent organic pollutants (POPs) is currently focused on chemicals emphasized in the Stockholm Convention. Quantitative detection of other substances (especially those with numerous anthropogenic sources such as polyaromatic hydrocarbons (PAHs)) is, however, also needed since their concentrations are usually several orders of magnitude higher. A goal of this study was to determine how various groups of compounds contribute to total human health risks at the variety of sampling sites in the region of Western Balkan. Distribution of the risks between the gas and particulate phases was also addressed. Results showed that inhalation exposure to organochlorine pesticides (OCPs) does not represent a significant risk to humans, while polychlorinated biphenyls (PCBs) re-volatilized to the atmosphere from contaminated soils and buildings can pose a problem. PCB evaporation from primary sources (currently used PCB-filled transformers or non-adequate storage facilities) generally resulted in much higher atmospheric concentrations than evaporation from the secondary sources (soils at the sites of war destructions). A majority of the human health risks at the urban sites were associated with PAHs. Between 83 and 94% of the cumulative risk at such sites was assigned to chemicals sorbed to particles, and out of it, PAHs were responsible for 99%.