Phytoextraction of Pb,Cr, Ni,and Zn using the aquatic plant Limnobium laevigatum and its potential use in the treatment of wastewater

In order to study the bioaccumulation of Pb, Cr, Ni, and Zn and the stress response, the floating aquatic plant Limnobium laevigatum was exposed to increasing concentrations of a mixture of these metals for 28 days, and its potential use in the treatment of wastewater was evaluated. The metal concentrations of the treatment 1 (T1) were Pb 1 μg L⁻¹, Cr 4 μg L⁻¹, Ni 25 μg L⁻¹, and Zn 30 μg L⁻¹; of treatment 2 (T2) were Pb 70 μg L⁻¹, Cr 70 μg L⁻¹, Ni 70 μg L⁻¹, and Zn 70 μg L⁻¹; and of treatment 3 (T3) were Pb 1000 μg L⁻¹, Cr 1000 μg L⁻¹, Ni 500 μg L⁻¹, and Zn 100 μg L⁻¹, and there was also a control group (without added metal). The accumulation of Pb, Cr, Ni, and Zn in roots was higher than in leaves of L. laevigatum, and the bioconcentration factor revealed that the concentrations of Ni and Zn in the leaf and root exceeded by over a thousand times the concentrations of those in the culture medium (2000 in leaf and 6800 in root for Ni; 3300 in leaf and 11,500 in root for Zn). Thus, this species can be considered as a hyperaccumulator of these metals. In general, the changes observed in the morphological and physiological parameters and the formation of products of lipid peroxidation of membranes during the exposure to moderate concentrations (T2) of the mixture of metals did not cause harmful effects to the survival of the species within the first 14 days of exposure. Taking into account the accumulation capacity and tolerance to heavy metals, L. laevigatum is suitable for phytoremediation in aquatic environments contaminated with moderated concentrations of Cr, Ni, Pb, and Zn in the early stages of exposure.

     

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.     

AnSBBR applied to the treatment of wastewater from a personal care industry: Effect of organic load and fill time

The objective of this work was to study the technological feasibility of treating wastewater from a personal care industry (PCI-WW) in a mechanically stirred anaerobic sequencing batch biofilm reactor (AnSBBR) containing immobilized biomass on polyurethane foam. An assessment was made on how system efficiency and stability would be affected by: increasing organic load; supplementation of nutrients and alkalinity; and different feed strategies. The AnSBBR operated with 8-h cycles, stirring speed of 400 rpm, temperature of 30 °C, and treated with 2.0 L wastewater per cycle. First the efficiency and stability of the AnSBBR were studied when submitted to an organic loading rate (OLR) of 3.1–9.4 gCOD/(L d), and when the PCI-WW was supplemented with nutrients (sucrose, urea, trace metals) and alkalinity. The AnSBBR was shown to be robust and presented stability and removal efficiency exceeding 90%. At an OLR of 12.0 gCOD/(L d) efficiency became difficult to maintain due to the presence of commercial cleansers and disinfectants in the wastewater lots. In a subsequent stage the AnSBBR treated the wastewater supplemented with alkalinity, but with no nutrients at varying feed strategies and maintaining an OLR of approximately 9.0 gCOD/(L d). The first strategy consists of feeding 2.0 L of the influent batchwise [OLR of 9.4 gCOD/(L d)]. In the second 1.0 L of influent was fed-batchwise and an additional 1.0 L was fed fed-batchwise [OLR of 9.2 gCOD/(L d)], i.e., in relation to the first strategy the feed volume was maintained but supplied in different periods. In the third strategy 1.0 L of treated effluent was maintained in the reactor and 1.0 L of influent was fed fed-batchwise [OLR of 9.0 gCOD/(L d)], i.e., in relation to the first strategy the feed volume was different but the feed period was the same and the OLR was maintained by increasing the influent concentration. Comparison of the first and second strategies revealed that organic matter removal efficiency was unaffected (exceeding 90%). The third strategy resulted in a reduction in average removal efficiency from 91 to 83% when compared to the first one. A kinetic study resulted in first order kinetic parameters ranges from 0.42 to 1.46 h⁻¹ at OLRs from 3.1 to 12.0 gCOD/(L d), respectively, and the second feed strategy [OLR of 9.2 gCOD/(L d)] was shown to be the most favorable.     

Monitoring of polychlorinated biphenyl contamination and estrogenic activity in water, commercial feed and farmed seafood

We evaluated the concentration and congener distribution of seven "target" polychlorinated biphenyls (PCBs) present in water collected in different aquaculture farms of the Mediterranean area, commercial feeds, and farmed seafood. PCBs were present in feed and in tissues of all the analysed organisms at levels ranging from 1.96 ng g(-1) to 124.00 ng g(-1) wet weight, and in 10.5% of the water samples, at levels from under detection limit to 33.0 ng l(-1) with total PCB concentrations significantly higher in samples from the Tyrrhenian Sea than the Adriatic Sea. PCB congener distribution in tissues resembled that of feed, suggesting that commercial feed is an important source of PCBs. The estrogenicity of organic extracts of the samples was also evaluated by using an in vitro yeast reporter assay. Estrogenic activity higher than 10% of the activity induced by 10 nM 17 beta-estradiol was observed in 20.0% of seafood samples and 15.8% of water samples. Seafood and water samples from the Tyrrhenian Sea were more frequently estrogenic than the Adriatic ones (16.45 versus 4.08%). A significant correlation of total PCB concentrations on biological activity was observed for sea bass and mussels from the Adriatic Sea (p < 0.045 and p < 0.04, respectively), and for sea bass of the Tyrrhenian Sea (p = 0.05). These results indicate the need of an integral approach in the exposure assessment to potential toxic compounds for human via food.     

The equivalence of diffusive samplers to reference methods for monitoring O3, benzene and NO2 in ambient air

A study of the equivalence to the reference methods of the Radiello samplers for ozone (O(3)) and benzene as well as the membrane-closed Palmes tube (MCPT) for nitrogen dioxide (NO(2)) is presented. These samplers benefit from new model equations capable of estimating their uptake rate. For O(3), the aim here was to demonstrate the equivalence for the reference period of 8 h and 120 microg m(-3), the target value of the 3rd European Daughter Directive. For benzene, the demonstration of equivalence to the annual limit value of 5 microg m(-3) of the 2nd European Daughter Directive was examined. In the case of NO(2), the equivalence to the annual limit value of the 1st European Daughter Directive (40 microg m(-3)) was considered. Results show that the radial sampler for O(3) fails to meet the Data Quality Objective (DQO) for continuous monitoring. However, with an expanded uncertainty of less than 30%, the O(3) diffusive sampler fulfils the DQO for indicative measurements. For benzene, the Radiello sampler exposed for 7 days gave satisfying results showing the ability of the sampler to meet the DQO of the reference method. Nevertheless, the field tests should be complemented by measurements for a wider range of benzene concentrations. In the case of NO(2), all the results of the laboratory and field experiments respected the requirements necessary for the demonstration of equivalence. Overall, these findings thus show that the Radiello sampler and the MCPT are equivalent to the reference methods only for assessment of benzene and NO(2), respectively.     

Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide

The chemical degradation of the herbicide azimsulfuron was investigated in aqueous solutions at different pH values. The hydrolysis rate, determined by HPLC analyses, was pH dependent and was much faster in acidic than in neutral or weakly basic conditions. The metabolites formed at different pH values were compared with standards when possible or isolated and identified using ESI-LC-MS/MS, (1)H NMR and (13)C NMR. The two main products of hydrolysis in mild acidic solution were identified as 2-amino-4,6-dimethoxy-pyrimidine and 2-methyl-4-(2-methyl-2H-tetrazol-5-yl)-2H-pyrazole-3-sulfonamide, both produced as a result of the sulfonylurea bridge cleavage. Under basic conditions, a new product, a substituted 2-pyrimidinamine, deriving from the contraction of the sulfonylurea bridge, was isolated and completely characterized for the first time.     

Possible effects of persistent organochlorinated pollutants cocktail on thyroid hormone levels and pituitary-thyroid interrelations

In polluted district of Michalovce in East Slovakia (POLL) and two districts with background pollution (BCGR) 2046 adults (834 males and 1212 females aged 20-75 years) were examined. Serum levels of thyrotropin (TSH), free thyroxine (FT4), total triiodothyronine (TT3) and antithyroperoxidase antibodies (TPOab) were estimated by electrochemiluminiscent assay and also these of 15 polychlorinated biphenyl congeners (PCBs), p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane were measured by high resolution gas chromatography/mass spectrometry. In addition, also dioxins, furans, coplanar- and mono-ortho-PCBs as well as selected hydroxylated and methylsulphonated PCBs and DDE metabolites were measured by appropriate methods based on gas chromatography/mass spectrometry principle. In POLL significantly higher levels of all organochlorines were found than these in BCGR. When pooled values from both areas were stratified in terms of PCBs level and treated as continuous variables, positive association of PCBs with FT4 and TT3 was found, the latter two being also mutually associated. However, within the category of PCBs level <530 ng/glipid (n=232) the association between PCBs and both the FT4 (p<0.09) and TT3 (p<0.03) was negative and any association of these was not found within the category of PCBs level of 531-1000 ng/g (n=691). In contrast, in the category of 531-2000 ng/g (n=1307) positive association appeared between PCBs and FT4 (p<0.001) as well as TT3 (p<0.05). Highly significant association of PCBs with FT4 (p<0.001) was further found in the categories with PCBs level of 1001-101414 ng/g (n=1307) and 2001-101414 (n=1123), while significant association with TT3 was observed only in the category of 531-2000 ng/g. Such findings suggest possible threshold level in positive effect of PCBs on FT4 and TT3 level which seems to be individual and located somewhere around the PCBs level of 1000 ng/g. However, highly significant negative association of both FT4 and TT3 with TSH was found in each of above indicated PCBs categories. Considerable difference in FT4 and TT3 level between large groups of subjects with the same range of PCBs level was also found suggesting different individual susceptibility to the effects of organochlorines. Among a total of 26 cases from POLL with very low TSH level (<0.5 mU l(-1)) 13 cases showed very high level of PCBs, FT4 and TT3, thus supporting a hypothesis on a novel sporadic form of high PCBs related peripheral subclinical hyperthyroidism possibly resulting from the long-term disruption of equilibrium between bound and free thyroxine in plasma by high PCBs level followed by a striking inhibition of TSH release from the pituitary.     

Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid

A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) (13)C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time (T(CH)) and proton spin-lattice relaxation time in the rotating frame (T(1rho)(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T(CH) values and the longest T(1rho)(H) values which suggested, respectively, one. an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two. consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T(CH) values and shorter T(1rho)(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.     

Assessment of global bioenergy potentials

So far, various studies assessed global biomass potentials and came up with widely varying results. Existing potential estimates range from 0 EJ/a up to more than 1,550 EJ/a which corresponds to about three times the current global primary energy consumption. This paper provides an overview of the available research on bioenergy potentials and reviews the different assessments qualitative way with the objective to interpret previous research in an integrated way. In the context of this paper we understand bioenergy as energy from biomass sources including energy crops, residues, byproducts and wastes from agriculture, forestry, food production and waste management. In this review special attention was paid to the difference between residue and energy potentials, land availability estimates, and the geographical resolution of existing potential estimates. The majority of studies concentrate on energy crop potentials retrieved from surplus agricultural land and only few publications assess global potentials separated by different world regions. It results that land allocated to the exclusive production of energy crops varies from 0 to 7,000 ha, depending on land category and scenario assumptions. Only a small number of available potential assessments consider residue potentials as well as energy crop potentials from degraded land. Future energy crop potentials are assumed to vary in the mean from 200 to 600 EJ/yr. In contrast residue potentials are expected to contribute between 62 and 325 EJ/yr. The highest potentials are assigned to Asia, Africa and South America while Europe, North America and the Pacific region contribute minor parts to the global potential.