Kinetic and chemical assessment of the UV/H2O2 treatment of antiepileptic drug carbamazepine

The UV/H2O2-induced degradation of carbamazepine, a worldwide used antiepileptic drug, recently found as contaminant in many municipal sewage treatment plant (STP) effluents and other aquatic environments, is investigated. The oxidation treatment caused an effective removal of the drug. At complete abatement of the substrate after 4 min treatment, a 35% value of removed total organic carbon (TOC) was obtained. A kinetic constant of (2.05+/-0.14) x 10(9) lmol(-1)s(-1) was determined for OH radical attack to carbamazepine in the UV/H2O2 process. Preparative TLC of the reaction mixture led to the isolation of acridine-9-carboxaldehyde as a reaction intermediate. HPLC and GC/MS analysis indicated formation of small amounts of acridine, salicylic acid, catechol and anthranilic acid among the reaction products. Under the same reaction conditions, synthetically prepared 10,11-epoxycarbamazepine was easily degraded to acridine as main product, suggesting that this epoxide is a likely intermediate in the oxidative conversion of carbamazepine to acridine. Under sunlight irradiation, carbamazepine in water underwent slow degradation to afford likewise acridine as main product. In view of the mutagenic properties of acridine, these results would raise important issues concerning the possible environmental impact of carbamazepine release through domestic wastewaters and support the importance of prolonged oxidation treatments to ensure complete degradation of aromatic intermediates.     

A field study of triclosan loss rates in river water (Cibolo Creek, TX)

Triclosan (TCS) is an anti-microbial agent used in down-the-drain consumer products. Following sewage treatment some of the triclosan will enter receiving waters. This study was designed to determine the die-away rate of triclosan released into a river as part of the sewage treatment plant effluent matrix. The study was conducted in Cibolo Creek, a moderate sized stream (discharge approximately 0.1 m(3)s(-1)) located in South Central Texas. Triclosan was analyzed from samples collected upstream of the sewage treatment plant, the sewage treatment plant effluent, and the river downstream from the effluent discharge. The first-order loss rate of parent triclosan from the water column was calculated from measured data (0.06 h(-1)) and this rate corresponded to a 76% reduction in triclosan over an 8 km river reach below the discharge. Mathematical modeling indicated that sorption and settling accounted for approximately 19% of total triclosan loss over 8 km. When removing sorption and settling, the remaining amount of triclosan had an estimated first-order loss rate of 0.25 h(-1). This loss rate was presumably due to other processes such as biodegradation and photolysis. These data show that loss of parent triclosan from the water column is rapid. Additional data are needed to fully document loss mechanisms.     

The effects of coal dust on photosynthetic performance of the mangrove, Avicennia marina in Richards Bay, South Africa

Richards Bay, on the northern KwaZulu-Natal coast, is the largest coal exporting port in South Africa. The coal is stored at the Richards Bay Coal Terminal (RBCT) prior to export. Dust from coal operations is a major problem in the Richards Bay area. In this study, we tested the hypothesis that coal dust adversely affects photosynthetic performance of Avicennia marina (Forssk.) Vierh., the dominant mangrove species in the harbour. Photosynthetic performance was determined on 10 trees by measuring carbon dioxide uptake and chlorophyll fluorescence parameters at two elevation sites and on upper and lower leaf surfaces that were covered or uncovered with coal dust. Measurements were made on five clear, sunny days at saturating light (>1,000 micromol m(-2)s(-1)) and high temperature (28-30 degrees C). Coal dust significantly reduced carbon dioxide exchange of upper and lower leaf surfaces by 17-39%, the reduction being generally greater on the lower leaf surface that is covered by a dense mat of trichomes and salt glands. The reduction in carbon dioxide exchange by coal dust was higher at the high elevation site that supported isolated dwarfed trees. The chlorophyll fluorescence data indicated that leaves coated with dust exhibited significantly lower photosystem II (PS II) quantum yield, lower electron transport rate (ETR) through PSII and reduced quantum efficiency of PSII (FvFm). The chlorophyll fluorescence data supported the gas exchange measurements and are consistent with reduced photosynthetic performance of leaves coated with coal dust.     

Degradation of terbutylazine (2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (2-chloro-4,6-dimethoxy-1,3,5-triazine) by zero valent iron and electrochemical reduction

To help elucidate the mechanism of dechlorination of chlorinated triazines via metallic iron, terbutylazine (TBA: 2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (DIA: 2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (CDMT: 2-chloro-4,6-dimethoxy-1,3,5-triazine) were degraded via zero valent iron under controlled pH conditions. The lower the solution pH the faster the degradation, with surface area normalized pseudo first order rate constants ranging from 2 (+/- 1)x10(-3) min(-1) m(-2) l for TBA at pH 2.0 to 4 (+/- 2)x10(-5) min(-1) m(-2) l for CDMT at pH 4.0. Hydrogenolysis (dechlorinated) products were observed for TBA and CDMT. Electrochemical reduction on mercury showed similar behavior for all of the triazines studied; the initial product of CDMT bulk electrolysis was the dechlorinated compound. The iron results are consistent with a mechanism involving the addition of surface hydrogen to the surface associated triazine.     

Simulated distributions of Baltic Sea-ice in warming climate and consequences for the winter habitat of the Baltic ringed seal

Sea-ice in the Baltic Sea in present and future climates is investigated. The Rossby Centre Regional Atmosphere-Ocean model was used to perform a set of 30-year-long time slice experiments. For each of the two driving global models HadAM3H and ECHAM4/OPYC3, one control run (1961-1990) and two scenario runs (2071-2100) based upon the SRES A2 and B2 emission scenarios were conducted. The future sea-ice volume in the Baltic Sea is reduced by 83% on average. The Bothnian Sea, large areas of the Gulf of Finland and Gulf of Riga, and the outer parts of the southwestern archipelago of Finland will become ice-free in the mean. The presented scenarios are used to study the impact of climate change on the Baltic ringed seal (Phoca hispida botnica). Climate change seems to be a major threat to all southern populations. The only fairly good winter sea-ice habitat is found to be confined to the Bay of Bothnia.     

Comparison of the adsorption of lead,cadmium, copper,zinc and barium to freshwater surface coatings

Measurements were made regarding the adsorption of lead, cadmium, copper, zinc and barium to freshwater surface coatings (biofilms and associated minerals), which were collected in Nanhu Lake in Jilin Province, PR China, in order to investigate the variability of adsorption capacities of these heavy metals mentioned in the above surface coatings. The adsorption of lead and other heavy metals to the biofilms was observed to decrease in the following order: copper, lead, zinc, cadmium, and barium. Generally, the values of Gamma(max) (the maximum adsorption, micromol/m(2)) increased with the standard electrode potential of metal elements used and were recorded as 166.7, 40.0, 29.4, 10.8, and 1.8 for copper, lead, zinc, cadmium and barium, respectively. The values of 1/Gamma(max) increased linearly with the decrease in values of the standard electrode potential of metal elements with a significant correlation (n=5, p=0.01) and increased linearly with the increase in values of covalent radius of metal elements with a significant correlation (n=5, p=0.05). This indicates that standard electrode potential and covalent radius were two of the principal characteristics of metals employed, causing the variation of lead and other heavy metal adsorption to the surface coatings.     

Bioindicators of enhanced nitrogen deposition

Increased deposition of atmospheric N largely from intensive agriculture is affecting biodiversity and the composition of natural and semi-natural vegetation in Europe. The value of species based bioindicators such as the Ellenberg N index and measurements of total tissue N and free amino acids in key plant species, is described with reference to a mixed woodland downwind of a livestock farm in the Scottish Borders, operated for over 20 years with a measured spatial gradient of ammonia concentration (29-1.5 microg m(-3)). All the indicators examined showed a relationship with N deposition and provided some indication of vegetation change. Total tissue N and arginine concentrations were most closely linked with ammonia concentrations and N deposition, with r(2) values of >0.97 and >0.78 respectively.     

Toxicity and heavy metal contamination of surficial sediments from the Bay of Thessaloniki (Northwestern Aegean Sea) Greece

Surficial sediments (the fraction < 2000 microm) from the Bay of Thessaloniki, in the Northwestern Aegean Sea, Greece were examined for heavy metal and organic carbon contents, as well as for acute LUMIStox toxicity of pore waters (PWs), wet sediment elutriates (WSEs) and dry sediment elutriates (DSEs) obtained from the solid material remaining after PW extraction. WSEs where not toxic. EC20/50 values could be measured in some DSE and PW samples. In all sediment samples, the DSE toxicity was greater than the corresponding PW toxicity. Sediment concentrations of total and labile Cd, Pb, Cu, Cr, Zn, Mn, Ni and Fe were determined and evaluated in relation to sediment quality guidelines. Pollution levels ranged from low to high for certain metals. A misfit between sediment toxicities calculated from heavy metal concentrations and those biologically measured was observed. Toxicity values were in general poorly correlated with sediment's heavy metal or organic carbon content. As significant correlation was however found between the DSE toxicity with total Ni and labile Fe, as well as for the PW toxicity with total Ni, labile Fe and labile Cr.     

Environmental contaminants and biochemical response in eel exposed to Po river water

Groups of eels (Anguilla anguilla) were exposed to Po river water under control conditions at "la Casella" Fluvial Hydrobiology Station for 30-day periods between November and May. At the end of the exposure period, fish were sacrificed and cytochrome P4501A was evaluated in liver microsomes using both catalytic (EROD) and semiquantitative immunodetection (ELISA) assays. At the same time, water samples were taken for chemical analyses of PCBs, PAHs and pesticides. Eel was chosen as bio-indicator on the bases of experiments on cytochrome P450 expression and activity under basal or induced conditions and in consideration of the ecological and economic relevance and ease of handling. Low levels of cytochrome P450 during Winter were followed by a step increase during Spring, associated with a substantial concentration increase of agrochemicals. A good correlation was found between measurements of cytochrome P4501A by EROD and ELISA in dose-effect experiments, however, ELISA showed a higher sensitivity. Immunochemical techniques may be used in addition to enzyme activity measurements both to detect lower levels of cytochrome P450 induction (where they proved more sensitive) and as quality control. These results suggest that measurement of cytochrome P4501A under controlled conditions, using eel as bio-indicator, can be a useful tool in monitoring Po river ecosystems.