Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.     

Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil

Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase in target plants. Although it has been used since 2000, only a limited number of degrading microorganisms have been reported. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione. Mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. LC-MS/MS analyses indicated that mesotrione degradation produced intermediates other than 2-amino-4-methylsulfonyl benzoic acid or 4-methylsulfonyl-2-nitrobenzoic acid, two metabolites previously identified in a mesotrione-degrading Bacillus strain. Since P. ananatis rapidly degraded mesotrione, this strain might be useful for bioremediation purposes.     

Investigations on the interaction of the phototoxic alkaloid coralyne with serum albumins

The interaction of the phototoxic alkaloid coralyne with bovine and human serum albumins (BSA, HSA) was investigated. Absorbance and fluorescence quenching experiments revealed the formation of strong complexes. Based on the binding parameters calculated from Stern-Volmer quenching method, coralyne has higher affinity to BSA (∼10⁵ M⁻¹) compared to HSA (∼10⁴ M⁻¹). Forster resonance energy transfer studies showed that the specific binding distances between Trp (donor) of the proteins and coralyne (acceptor) were 2.95 and 3.10 nm, respectively. The bindings were favored by negative enthalpy and a stronger favorable entropy contribution. The heat capacity values for binding to BSA and HSA were similar, indicating the involvement of similar molecular forces in the complexation. Competitive binding experiments using site markers demonstrated that coralyne binds to site I (subdomain IIA) of both proteins. The secondary structure of the proteins was altered, suggesting a small but definitive partial unfolding on complexation.     

Chlorinated solvents in a petrochemical wastewater treatment plant: an assessment of their removal using self-organising maps

The self-organising map approach was used to assess the efficiency of chlorinated solvent removal from petrochemical wastewater in a refinery wastewater treatment plant. Chlorinated solvents and inorganic anions (11 variables) were determined in 72 wastewater samples, collected from three different purification streams. The classification of variables identified technical solvents, brine from oil desalting and runoff sulphates as pollution sources in the refinery, affecting the quality of wastewater treatment plant influent. The classification of samples revealed the formation of five clusters: the first three clusters contained samples collected from the drainage water, process water and oiled rainwater treatment streams. The fourth cluster consisted mainly of samples collected after biological treatment, and the fifth one of samples collected after an unusual event. SOM analysis showed that the biological treatment step significantly reduced concentrations of chlorinated solvents in wastewater.     

Electrogeneration of H(2) for Pd-catalytic hydrodechlorination of 2,4-dichlorophenol in groundwater

A novel electrolytic groundwater remediation process, which used the H₂ continuously generated at cathode to achieve in situ catalytic hydrodechlorination, was developed for the treatment of 2,4-dichlorophenol (2,4-DCP) in groundwater. Catalytic hydrodechlorination using Pd supported on bamboo charcoal and external H₂ showed that 2,4-DCP was completely dechlorinated to phenol within 30 min at pH ? 5.5. In a divided electrolytic system, the catalytic hydrodechlorination of 2,4-DCP in cathodic compartment by H₂ generated at the cathode under 20 and 50 mA reached 100% at 120 and 60 min, respectively. Two column experiments with influent pHs of 5.5 (unconditioned) and 2 were conducted to evaluate the feasibility of this process. The 2,4-DCP removal efficiencies were about 63% and nearly 100% at influent pHs of 5.5 and 2, respectively. Phenol was solely produced by 2,4-DCP hydrodechlorination, and was subsequently degraded at the anode. A low pH could enhance the hydrodechlorination, but was not necessarily required. This study provides the preliminary results of a novel effective electrolytic process for the remediation of groundwater contaminated by chlorinated aromatics.     

Nitrogen fertilizer improves boron phytoextraction by Brassica juncea grown in contaminated sediments and alleviates plant stress

In this study we evaluated the effect of different fertilizer treatments on Brassica plants grown on boron-contaminated sediments. Experiments were conducted in the laboratory and on the lysimeter scale. At laboratory scale (microcosm), five different fertilizers were tested for a 35-d period. On the lysimeter scale, nitrogen fertilization was tested at three different doses and plants were allowed to grow until the end of the vegetative phase (70 d). Results showed that nitrogen application had effectively increased plant biomass production, while B uptake was not affected. Total B phytoextracted increased three-fold when the highest nitrogen dose was applied. Phytotoxicity on Brassica was evaluated by biochemical parameters. In plants grown in unfertilized B-contaminated sediments, the activity of antioxidant enzymes superoxide dismutase (SOD), ascorbate peroxidase (APX) and pyrogallol peroxidase (PPX) increased, whereas catalase (CAT) decreased with respect to control plants. Addition of N progressively mitigated the alteration of enzymatic activity, thus suggesting that N can aid in alleviating B-induced oxidative stress. SOD activity was restored to control levels just at the lowest N treatment, whereas the CAT inhibition was partially restored only at the highest one. N application also lowered the B-induced increase in APX and PPX activities. Increased glutathione reductase activity indicated the need to restore the oxidative balance of glutathione. Data also suggest a role of glutathione and phytochelatins in B defense mechanisms. Results suggest that the nitrogen fertilizer was effective in improving B phytoextraction by increasing Brassica biomass and by alleviating B-induced oxidative stress.     

Estimation of thyroid doses and health risks resulting from the intake of radioactive iodine in foods and drinking water by the citizens of Tokyo after the Fukushima nuclear accident

The release of radioactive materials from the Fukushima nuclear power plant after the Great East Japan Earthquake on 11 March 2011 poses health risks. In this study, the intake of iodine 131 (I-131) in drinking water and foods (milk, dairy products, and vegetables) by citizens of Tokyo was estimated. The effects of countermeasures (restrictions on the distribution of foods and the distribution of bottled water for infants) on reducing intake were also evaluated. The average thyroid equivalent doses without countermeasures from 21 March 2011 were 0.42 mSv in adults, 1.49 mSv in children, and 2.08 mSv in infants. Those with countermeasures were 0.28, 0.97, and 1.14 mSv respectively, reductions of 33%, 35%, and 45%. Drinking water contributed more to intake by adults and children than foods. The intake of I-131 within the first 2 weeks was more than 80% of the estimated intake, owing to its short half-life, indicating that rapid countermeasures are important in reducing intake. The average risks of cancer incidence and mortality due to I-131 for infants were estimated to be 3 × 10⁻⁵ and 0.2 × 10⁻⁵, respectively, lower than the annual risks of traffic accidents, naturally occurring radioactive material (potassium 40), and environmental pollutants such as diesel exhaust particles.     

Partitioning of Cd and Pb in the blood of European blackbirds (Turdus merula) from a smelter contaminated site and use for biomonitoring

Blood composition is commonly measured to assess exposure to and effects of metals on birds. In most of passerine species, only small volumes of blood may be sampled safely (<500 μL), which limit the measure of several markers of health status and chemical residues. Here, we documented the partitioning of Cd and Pb in the blood of European Blackbirds Turdus merula in order to propose usable relationships between whole blood concentrations (for which toxicological benchmarks exist) and those measured in the erythrocytes. Sixty-two blackbirds were trapped along a pollution gradient (smelter of Metaleurop Nord, Northern France). Blood was sampled and Cd and Pb concentrations were measured both in whole blood and in the erythrocytes only. Birds coming from the most contaminated sites exhibited high residues for both Cd and Pb. We assessed that 73% and 99% of Cd and Pb, respectively, were associated to erythrocytes. Strong linear relationships, that were not influenced by neither the age nor the sex, were established between whole blood residues and those of erythrocytes for Cd and Pb (adj-R² = 0.78 and 0.93, respectively). Present findings are promising to optimize the use of small blood samples in order to investigate several responses relative to wildlife health status.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

Chronic toxicity of copper on embryo development in Chinese toad, Bufo gargarizans

This study examined the effects of copper exposure on embryonic development of Chinese toad, Bufo gargarizans. Firstly, the LC₅₀ values from 24 to 96 h of exposure were 3.61 × 10⁻⁶ M, by means of a 4 d toxicity test with B. gargarizans embryos. Secondly, Chinese toad embryos were exposed to 10⁻⁹-10⁻⁶ M copper from mid gastrula stage to operculum completion stage. Measurements included mortality, tadpole weight, tadpole total length, growth retardation, duration of different embryo stages and malformation. Embryonic survival was not affected by copper. Relative to control tadpoles, significantly decreased weight and total length were found at 10^-9-10^-6 M reduced percentage of the embryos in right operculum stage after 10 d exposure to copper and reduced percentage of embryos in operculum completion stage after 12 d exposure to copper were also observed. Moreover, the duration of embryonic development increased at neural, circulation and operculum development stage in copper-treated groups. For the scanning microscope and histological observation, the abnormalities were malformation of wavy dorsal fin, flexural tail, curvature body axis, yolk sac oedema and reduced pigmentation in the yolk sac. Histopathological changes in olfactory, retinal epithelium and skin were also observed. DNA strand breaks exposed to the copper were analyzed by DNA ladder. In conclusion, copper induced toxic effects on B. gargarizans embryos. The present study indicated chronic toxicity tests may provide more accurate way in formulating the “safe levels” of heavy metals to amphibian.