Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

Diffusion pollution from livestock and poultry rearing in the Yangtze Delta,China

BACKGROUND: The Yangtze Delta is one of the most developed regions in China and includes Shanghai, eight cities in Jiangsu province and eight cities in Zhejiang province. Meat consumption in this region has increased with economic growth, and most of the consumed meat is produced locally. The water quality of surface waters has deteriorated in recent years. An example was the huge blue-green algae bloom in Tai Lake in late May 2007, which affected millions of people's daily drinking water. However, animal husbandry is considered to be one of the main pollution sources. METHODS: Pollutants (NH3-N, total phosphorus (TP), and total nitrogen (TN)) excreted by livestock and poultry, and the resultant COD (chemical oxygen demand) and BOD (biochemical oxygen demand), were estimated using two different methods based on different data sets. RESULTS: The number of livestock and poultry has remained stable in the Yangtze Delta over the four years from 1999 to 2002, with the average number of pigs, cattle, sheep and poultry being 21.1 M, 0.4 M, 7.7 M and 597.6 M, respectively. Pollutants in livestock and poultry excreta estimated by Method I were: 0.12 Mt NH3-N, 0.11 Mt TP and 0.29 Mt TN, resulting in COD and BOD of 1.34 Mt and 1.30 Mt, respectively, while the estimations based on Method II were: 0.18 Mt NH3-N, 0.15 Mt TP and 0.40 Mt TN, resulting in COD and BOD of 1.95 Mt and 1.80 Mt, respectively. DISCUSSION: Pollutants excreted annually by livestock and poultry in the Yangtze Delta are estimated to be: 0.17 Mt NH3-N, 0.16 Mt TP and 0.42 Mt TN, giving rise to a COD of 1.86 Mt and a BOD of 1.72 Mt. Approximately 25% of this pollution was estimated to enter water bodies, which means that the annual pollutant load is 43,700 t NH3-N, 39,400 tTP, 104,600t TN with a COD of 465,000 tand a BOD of 430,100 t. Pollutants from animal husbandry were similar in magnitude to those from industrial wastewater. Pigs produced the most pollution, followed by poultry, cattle and sheep. The pollution load from animal husbandry in the Yangtze Delta is about twice the average level of the whole of China. CONCLUSIONS: Domestic wastewater was the main pollution source in the Yangtze Delta, followed by pollution from raising livestock and poultry and from industrial wastewater. The pollution load in Shanghai and Jiaxing were the greatest, followed by 7 cities of Jiangsu province (except Suzhou) and other cities of Zhejiang province and Suzhou. Pigs and poultry produced about 90% of the total pollutants from animal husbandry. RECOMMENDATIONS AND PERSPECTIVES: The local governments, especially in Shanghai and Jiaxing, should focus their attention on the pollution produced by livestock and poulrry. Controlling pollution from pigs and poultry will have the greatest impact in this region. Control of pollution will be facilitated by the development of large-scale livestock and poultry farming units and a shift away from small scale husbandry.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

The zebrafish embryo model in environmental risk assessment—applications beyond acute toxicity testing

BACKGROUND, AIM, AND SCOPE: The use of fish embryos is not regulated by current legislations on animal welfare and is therefore considered as a refinement, if not replacement of animal experiments. Fish embryos represent an attractive model for environmental risk assessment of chemicals since they offer the possibility to perform small-scale, high-throughput analyses. MAIN FEATURES: Beyond their application for determining the acute toxicity, fish embryos are also excellent models for studies aimed at the understanding of toxic mechanisms and the indication of possible adverse and long-term effects. Therefore, we have reviewed the scientific literature in order to indicate alternative applications of the fish embryo model with focus on embryos of the zebrafish. RESULTS AND DISCUSSIONS: The analysis of the mode of action is important for the risk assessment of environmental chemicals and can assist in indicating adverse and long-term effects. Toxicogenomics present a promising approach to unravel the potential mechanisms. Therefore, we present examples of the use of zebrafish embryos to study the effect of chemicals on gene and protein patterns, and the potential implications of differential expression for toxicity. The possible application of other methods, such as kinase arrays or metabolomic profiling, is also highlighted. Furthermore, we show examples of toxicokinetic studies (bioconcentration, ABC transporters) and discuss limitations that might be caused by the potential barrier function of the chorion. Finally, we demonstrate that biomarkers of endocrine disruption, immune modulation, genotoxicity or chronic toxicity could be used as indicators or predictors of sub-acute and long-term effects. CONCLUSIONS: The zebrafish embryo represents a model with an impressive range of possible applications in environmental sciences. Particularly, the adaptation of molecular, system-wide approaches from biomedical research is likely to extend its use in ecotoxicology. RECOMMENDATIONS AND PERSPECTIVES: Challenges for future research are (1) the identification of further suitable molecular markers as indicators of the mode of action, (2) the establishment of strong links between (molecular) effects in short-term assays in embryos and long-term (toxic) effects on individuals, (3) the definition of limitations of the model and (4) the development of tests that can be used for regulatory purposes.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Characterization of the toxic effects of cadmium and 3.5-dichlorophenol on nitrifying activity and mortality in biologically activated sludge systems—effect of low temperature

Background, aims, and scope  Sometimes, urban wastewaters convey a more or less significant part of toxic products from industries or the craft industry. Nitrifying activity can be affected by these substances, implying higher ammonia concentrations in the outlet effluent and contributing to toxicity for the aquatic environment. Moreover, the more stringently treated wastewater standards now require a reliable treatment for nitrogen. One of the key issues is the identification of the inhibition behavior of nitrifying bacteria facing a toxic substance. This new understanding could then finally be integrated into models in order to represent and to optimize wastewater treatment plants (WWTP) operation in cases involving ‘toxic scenarios’. Materials and methods  The toxic substances studied in this work, cadmium and 3.5-dichlorophenol (3.5-DCP), are representative of chemical substances commonly found in municipal sewage and industrial effluents and symbolize two different contaminant groups. The effects of Cd and 3.5-DCP on nitrification kinetics have been investigated using respirometry techniques. Results  IC50 values determination gives concentrations of 3.1 mg/L for 3.5-DCP and 45.8 mg/L for Cd at 21 ± 1°C. The variation to low temperature seems to have no real effect on IC50 for DCP, but induces a decrease of cadmium IC50 to 27.5 mg/L at 14°C. Finally, specific respirometric tests have been carried out in order to determine the potential effect of these toxic substances on the nitrifying decay rate b _a . No significant effect has been noticed for Cd, whereas the presence of 3.5-DCP (at IC50 concentration) induced a dramatic increase of b _a at 20°C. The same behavior has been confirmed by experiments performed in winter periods with a sludge temperature around 12°C. Discussion  The target substances have different modes of action on activity and mortality, notably due to the abilities of the contaminant to be precipitated, accumulated, or even to be progressively degraded. Studies realized at low temperature confirmed this assumption, and put in evidence the effect of temperature on toxic substances capable of being biosorbed. However, the change in the sludge sample characteristics can be pointed out as a problem in the investigation of the temperature effect on nitrification inhibition, as biosorption, bioaccumulation, and predation are directly linked to the sludge characteristics (VSS concentration, temperature) and the plant operating conditions (loading rates, sludge age, etc.). Conclusions  This work brings new understandings concerning the action mode of these specific contaminants on nitrifying bacteria and, in particular, on the role of temperature. The experiments lead to the determination of the IC50 values for both toxic substances on biological nitrification. The inhibition mechanisms of Cd and 3.5-DCP on nitrifying activity have been simply represented by a non-competitive inhibition model. Recommendations and perspectives  Other experiments carried out in a continuous lab-scale pilot plant should be done with a proper control of the operating conditions and of the sludge characteristics in order to better understand the mechanisms of nitrification inhibition for each contaminant. Finally, these first results show that toxic substances can have an effect on the growth rate but also on the decay rate, depending on the characteristics of the toxic substance and the sludge. This eventual double effect would imply different strategies of WWTP operation according to the behavior of the contaminant on the bacteria.     

Recent advances in the photocatalytic reduction of carbon dioxide

Fossil fuels are currently the major energy source and are rapidly consumed to supply the increasing energy demands of mankind. CO₂, a product of fossil fuel combustion, leads to climate change and will have a serious impact on our environment. There is an increasing need to mitigate CO₂ emissions using carbon–neutral energy sources. Therefore, research activities are devoted to CO₂ capture, storage and utilization. For instance, photocatalytic reduction of CO₂ into hydrocarbon fuels is a promising avenue to recycle carbon dioxide. Here we review the present status of the emission and utilization of CO₂. Then we review the photocatalytic conversion of CO₂ by TiO₂, modified TiO₂ and non-titanium metal oxides. Finally, the challenges and prospects for further development of CO₂ photocatalytic reduction are presented.