Revisiting the plant hyperaccumulation criteria to rare plants and earth abundant elements

The several established criteria to define a hyperaccumulator plant were applied to a rare and endangered species, Plantago almogravensis, and to the 3rd most abundant element in the earth crust, Al. Using the most common criteria, P. almogravensis undoubtedly is an Al hyperaccumulator plant. If the recent proposed requirements were considered, most of them matching those for a plant to be used in phytoextraction, it can only be considered an unusual accumulator of Al. A discussion is made concerning the several criteria of a hyperaccumulator plant in order to include rare and endemic ones and abundant elements. In ecological terms, the enrichment in Al and Fe observed may account for the differences in the vegetation pattern. Due to the rarity and endangered nature of this plant, the contribution of this work is also relevant for the ecological understanding and the development of conservation options of this endemic species.     

A fluorescence-based bioassay for aquatic macrophytes and its suitability for effect analysis of non-photosystem II inhibitors

Background, Goals and Scope During the last years the miniaturization of toxicity test systems for rapid and parallel measurements of large quantities of samples has often been discussed. For unicellular algae as well as for aquatic macrophytes, fluorescence-based miniaturized test systems have been introduced to analyze photosystem II (PSII) inhibitors. Nevertheless, high-throughput screening should also guarantee the effect detection of a broad range of toxicants in order to ensure routinely applicable, high-throughput measuring device experiments which can cover a broad range of toxicants and modes of action others than PSII inhibition. Thus, the aim of this study was to establish a fast and reproducible measuring system for non-PSII inhibitors for aquatic macrophyte species to overcome major limitations for use. Methods A newly developed imaging pulse-amplitude-modulated chlorophyll fluorometer (I-PAM) was applied as an effect detector in short-term bioassays with the aquatic macrophyte species Lemna minor. This multiwell-plate based measuring device enabled the incubation and measurement of up to 24 samples in parallel. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, polycyclic aromatic hydrocarbons (PAHs) and pharmaceuticals and personal care products (PPCPs), which are often detected in the aquatic environment. The I-PAM was used (i) to establish and validate the sensitivity of the test system to the three non-PSII inhibitors, (ii) to compare the test systems with standardized and established biotests for aquatic macrophytes, and (iii) to define necessary time scales in aquatic macrophyte testing. For validation of the fluorescence-based assay, the standard growth test with L. minor (ISO/DIS 20079) was performed in parallel for each chemical. Results The results revealed that fluorescence-based measurements with the I-PAM allow rapid and parallel analysis of large amounts of aquatic macrophyte samples. The I-PAM enabled the recording of concentration-effect-curves with L. minor samples on a 24-well plate with single measurements. Fluorescence-based concentration-effect-curves could be detected for all three chemicals after only 1 h of incubation. After 4–5 h incubation time, the maximum inhibition of fluorescence showed an 80–100% effect for the chemicals tested. The EC50 after 24 h incubation were estimated to be 0.06 mg/L, 0.84 mg/L and 1.69 mg/L for paraquatdichloride, alizarine and triclosan, respectively. Discussion The results obtained with the I-PAM after 24 h for the herbicide paraquat-dichloride and the polycyclic aromatic hydrocarbon alizarine were in good accordance with median effective concentrations (EC50s) obtained by the standardized growth test for L. minor after 7 d incubation (0.09 mg/L and 0.79 mg/L for paraquat-dichloride and alizarine, respectively). Those results were in accordance with literature findings for the two chemicals. In contrast, fluorescence-based EC50 of the antimicrobial agent triclosan proved to be two orders of magnitude greater when compared to the standard growth test with 7 d incubation time (0.026 mg/L) as well as with literature findings. Conclusion Typically, aquatic macrophyte testing is very time consuming and relies on laborious experimental set-ups. The I-PAM measuring device enabled fast effect screening for the three chemicals tested. While established test systems for aquatic macrophytes need incubation times of ≥ 7 d, the I-PAM can detect inhibitory effects much earlier (24 h), even if inhibition of chemicals is not specifically associated with PSII. Thus, the fluorescence-based bioassay with the I-PAM offers a promising approach for the miniaturization and high-throughput testing of chemicals with aquatic macrophytes. For the chemical triclosan, however, the short-term effect prediction with the I-PAM has been shown to be less sensitive than with long-term bioassays, which might be due to physicochemical substance properties such as lipophilicity. Recommendations and Perspectives The results of this study show that the I-PAM represents a promising tool for decreasing the incubation times of aquatic macrophyte toxicity testing to about 24 h as a supplement to existing test batteries. The applicability of this I-PAM bioassay on emergent and submerged aquatic macrophyte species should be investigated in further studies. Regarding considerations that physicochemical properties of the tested substances might play an important role in microplate bioassays, the I-PAM bioassay should either be accompanied by evaluating physicochemical properties modeled from structural information prior to an experimental investigation, or by intensified chemical analyses to identify and determine nominal concentrations of the toxicants tested. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, PAHs and PPCPs which are often detected in the aquatic environment. Nevertheless, in order to ensure a routinely applicable measuring device, experiments with a broader range of toxicants and samples of surface and/or waste waters are necessary. ESS-Submission Editor: Dr. Markus Hecker (MHecker@Entrix.com)     

Comparison of two metal surveys by moss Tortula ruralis in Budapest, Hungary

Moss transplants of Tortula ruralis were used as active biomonitoring organisms as part of a monitoring study to assess the metals (Al, Cd, Cu, Cr, Fe, Ni, Pb, V and Zn) associated with ambient particles on mosses in Budapest, the capital town of Hungary. The moss samples were collected in a nature conservation area from a semi-arid sand grassland (Festucetum vaginatae danubiale), less than 1 month before transplantation. Moss cushions were exposed to pollution in Budapest during October–November 1993 and February–March 1994. In the study area, 16 sites were marked out as measuring sites, in accordance with the structure of the city. A similar stand was established in the Botanical Gardens of the Szent István University in Gödöll? as a control site. ICP-AES analysis of moss for metals showed the ability of Tortula ruralis to accumulate the metals under study. Control site showed lower impact in comparison to the other sites.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Acid-base properties of humic substances from composted and thermally-dried sewage sludges and amended soils as determined by potentiometric titration and the NICA-Donnan model

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from composted sewage sludge (CS), thermally-dried sewage sludge (TS), soils amended with either CS or TS at a rate of 80 t ha(-1)y(-1) for 3y and the corresponding unamended soil were investigated by use of potentiometric titrations. The non-ideal competitive adsorption (NICA)-Donnan model for a bimodal distribution of proton binding sites was fitted to titration data by use of a least-squares minimization method. The main fitting parameters of the NICA-Donnan model obtained for each HA and FA sample included site densities, median affinity constants and widths of affinity distributions for proton binding to low and high affinity sites, which were assumed to be, respectively, carboxylic- and phenolic-type groups. With respect to unamended soil HA and FA, the HAs and FAs from CS, and especially TS, were characterized by smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, and smaller heterogeneity of carboxylic and phenolic-type groups. Amendment with CS or TS led to a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. These effects were more evident in the HA and FA fractions from CS-amended soil than in those from TS-amended soil.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

Polychlorinated biphenyls and DDT in swordfish (Xiphias gladius) and blue shark (Prionace glauca) from Brazilian coast

The polychlorinated biphenyls (PCBs) and DDT may bioaccumulate in the aquatic food web and have been of great concern due to their toxic effects on wildlife and human health. There is evidence showing that fish in the human diet contributes at a significant proportion to the total intake of PCBs and other organochlorine compounds, particularly fish with higher fat levels. This study investigated the concentration of PCBs and DDTs in muscle tissues of samples of the blue shark (Prionace glauca) and a swordfish (Xiphias gladius) from east Brazilian coast and estimate the human exposure to total DDTs through the consumption of both the species. Samples of the each species were caught between August and September 2001. The mean concentration for summation operator PCBs in P. glauca was 3.15 ng/g w.w. and the summation operator DDTs was 0.93 ng/g w.w. The mean concentration of summation operator PCBs in X. gladius was 6.50 ng/g and the mean of summation operator DDTs was 2.47 ng/g. The estimated daily intake of summation operator DDT through X. gladius or P. glauca consumption can be considered safe since it contributes to less than 0.1% of the limit of acceptable daily intake (ADI) of summation operator DDT proposed by WHO.     

Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SigmaPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SigmaPBDE concentration. The SigmaPBDE concentration had a highly significant correlation with SigmaPCB, SigmaCHL, dieldrin, HCB and SigmaHCH concentrations. We found a seasonal pattern of median SigmaPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.     

Exemplifying whole-plant ozone uptake in adult forest trees of contrasting species and site conditions

Whole-tree O3 uptake was exemplified for Picea abies, Fagus sylvatica and Larix decidua in stands at high and low altitude and contrasting water availability through sap flow measurement in tree trunks, intrinsically accounting for drought and boundary layer effects on O3 flux. O3 uptake of evergreen spruce per unit foliage area was enhanced by 100% at high relative to low elevation, whereas deciduous beech and larch showed similar uptake regardless of altitude. The responsiveness of the canopy conductance to water vapor and, as a consequence, O3 uptake to soil moisture and air humidity did not differ between species. Unifying findings at the whole-tree level will promote cause-effect based O3 risk assessment and modeling.