Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Estimation of critical loads for radiocaesium in Fennoscandia and Northwest Russia

The application of the critical loads methodology for radioactive contamination of Arctic and sub-arctic ecosystems, where natural and semi-natural food products are important components of the diet of many people, is proposed and discussed. The critical load is herein defined as the amount of radionuclide deposition necessary to produce radionuclide activity concentrations in food products exceeding intervention limits. The high transfer of radiocaesium to reindeer meat gives this product the lowest critical load, even though the intervention limit is relatively high compared with other products. Ecological half-lives of radiocaesium in natural and semi-natural products are often very long, and it is therefore important to take account of contamination already present in the event of an accident affecting areas where such products are important. In particular, the long ecological half-life for radiocaesium in moose meat means that the critical load is highly sensitive to prior deposition. An example of the potential application of the method for emergency preparedness is given for the Chernobyl accident.     

Transfer of 137Cs and 60Co from irrigation water to a soil-tomato plant system

An experiment has been performed at the nuclear power plant of Garigliano (Caserta, Italy), aiming at the measurement of transfer factors of 137Cs and 60Co radionuclides from the irrigation water to a soil-plant system, with particular attention to the influence on such transfers of the irrigation technique (ground or aerial). Tomato plants were irrigated weekly with water contaminated with 137Cs and 60Co (about 375 Bq/m2 week), using both irrigation techniques. After 13 weeks, fruits, leaves, stems, roots and soil were sampled, and radionuclide concentrations were measured by high-resolution gamma spectroscopy. It was found that the activity allocated to the plant organs is significantly dependent upon the irrigation technique, amounting to 2.1% and 1.6% of the activity given in the cultivation for aerial treatment and 0.4% and 0.3% for the ground treatment, for 137Cs and 60Co respectively. The activity absorbed by plants is allocated mainly in leaves (> 55%), while less then 10% is stored in the fruits, for both irrigation techniques. Transfer factors (soil-plant and irrigation water-plant) of tomato plants and of weeds have been determined for 137Cs and 60Co, as well as for natural 40K in the soil.     

A general methodology for structuring models to predict the long-term migration of radionuclides from catchments

In the present paper a generic model for predicting the long-term migration of radionuclides and heavy metals from catchments is described. The model subdivides the catchment into a number of homogeneous, infinitesimal sub-catchments and integrates the radionuclide contributions from such sub-catchments to calculate the total flux of contaminant. It relates the radionuclide behaviour to the statistical distribution of the pollutant partition coefficient on the "ensemble" of sub-catchments. The methodology was validated for 90Sr and 137Cs by using data for water contamination in some European rivers. Values of migration parameters for Pu, Tc, I and Cd isotopes were obtained.     

Radiation doses of Swiss population from external sources

The outdoor radiation exposure of the population in Switzerland from external sources results from cosmic background as well as from natural and artificial ground radiation. The geographical distribution of these components and of the total dose rate are represented on maps consisting of 2 kmx2 km grid cells. The average dose rate on Swiss territory outdoors is 147 nSv/h (1.29 mSv/a). The distributions are then related to the population density distribution by GIS application. The population is exposed to an average dose rate of 108 nSv/h (0.95 mSv/a) per capita which is just below the threshold for man-made dose rate given by national regulation. The lower value (relative to the country average 147 nSv/h) arises from the fact that most of the population lives north of the Alps where the lithology is dominated by rocks of relatively low radioactivity and where the cosmic radiation is low relative to the Alps.     

Global weapons' fallout 137Cs in soils and transfer to vegetation in south-central Chile

The contamination and depth distribution of 137Cs in soil due to the fallout from atmospheric weapons' tests were measured at 29 sites in the 9th and 10th administrative regions in Chile located in the 40 degrees latitude in the southern hemisphere. The depth distribution in most of the sites follows no systematic pattern in the upper few centimetres, but below this depth an exponential decline could be deduced. The calculated relaxation depth appears to be a good indicator for estimating the long-term 137Cs distribution in these soil profiles. It ranges from 4.4 +/- 1.9 cm in Palehumults to 8.4 +/- 4.4 and 9.7 +/- 5.1 cm in Hapludands and Psamments, respectively. For these soil types the value for the relaxation depth tends to increase with decreasing clay content and increasing volume of coarse pores. 137Cs activity densities at the selected sites ranged from 450 to 5410 Bq m(-2) and correlate significantly (r = 0.791) with the mean annual rainfall rate of the sampling sites. 137Cs concentration ratios of prairie plants/soil were found to be in the range 0.008-2.3 and could be related to relaxation depths in undisturbed soils.     

PM2.5 assessment in 21 European study centers of ECRHS II: Method and first winter results

The follow-up of a cohort of adults from 29 European centers of the former European Community Respiratory Health Survey (ECRHS) I (1989-1992) will examine the long-term effects of exposure to ambient air pollution on the incidence, course, and prognosis of respiratory diseases, in particular asthma and decline in lung function. The purpose of this article is to describe the methodology and the European-wide quality control program for the collection of particles with 50% cut-off size of 2.5 microm aerodynamic diameter (PM2.5) in the ECRHS II and to present the PM2.5 results from the winter period 2000-2001. Because PM2.5 is not routinely monitored in Europe, we measured PM2.5 mass concentrations in 21 participating centers to estimate background exposure in these cities. A standardized protocol was developed using identical equipment in each center (U.S. Environmental Protection Agency Well Impactor Ninety-Six [WINS] and PQ167 from BGI, Inc.). Filters were weighed in a single central laboratory. Sampling was conducted for 7 days per month for a year. Winter mean PM2.5 mass concentrations (November 2000-February 2001) varied substantially, with Iceland reporting the lowest value (5 microg/m3) and northern Italy the highest (69 microg/m3). A standardized procedure appropriate for PM2.5 exposure assessment in a multicenter study was developed. We expect ECRHS II to have sufficient variation in exposure to assess long-term effects of air pollution in this cohort. Any bias caused by variation in the characteristics of the chosen monitoring location (e.g., proximity to traffic sources) will be addressed in later analyses. Given the homogenous spatial distribution of PM2.5, however, concentrations measured near traffic are not expected to differ substantially from those measured at urban background sites.     

Aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in sediments collected from the 110 mile hole and along a transect from 58 degrees 58.32'N 1 degree 10.38'W to the inner Moray Firth,Scotland

Sediments were collected from the 110 mile hole and along a transect from 58 degrees 58.32' N 1 degree 10.38' W to the UK National Marine Monitoring (NMMP) site in the inner Moray Firth, for determination of hydrocarbon concentration and composition. Total PAH concentrations (2- to 6-ring PAHs, parent and branched) were highest at NMMP site 95 and at the associated end of the transect in the inner Moray Firth. PAHs in this area were of predominately pyrolytic origin and could be attributed to urban and industrial activities. The majority of sediments collected in the middle section of the transect had low total PAH concentrations (< 100 ng g(-1) dry weight). The high proportion of naphthalenes and alkylated PAHs in this area suggested a predominately petrogenic input. The GC-FID aliphatic hydrocarbon profiles showed that the majority of sediments, including those in the inner Firth, had a limited petrogenic input. This was supported by the geochemical biomarker profiles, which contained triterpanes typical of Middle Eastern crude oil. Principal component analysis was used to investigate spatial trends in the PAH distributions and demonstrated that there were differences between areas. The NMMP site 95 and transect start and middle sediments were well separated. PCA further confirmed that sediments from the NMMP site 95, the 110 mile hole and the inner Moray Firth (south west) end of the transect contained PAHs from predominately pyrolytic sources, whereas sediments from the north east end (start) and the middle of the transect were typified by a greater petrogenic component.     

Review and assessment of models used to predict the fate of radionuclides in lakes

A variety of models for predicting the behaviour of radionuclides in fresh water ecosystems have been developed and tested during recent decades within the framework of many international research projects. These models have been implemented in Computerised Decision Support Systems (CDSS) for assisting the appropriate management of fresh water bodies contaminated by radionuclides. The assessment of the state-of-the-art and the consolidation of these CDSSs has been envisaged, by the scientific community, as a primary necessity for the rationalisation of the sector. The classification of the approaches of the various models, the determination of their essential features, the identification of similarities and differences among them and the definition of their application domains are all essential for the harmonisation of the existing CDSSs and for the possible development and improvement of reference models that can be widely applied in different environmental conditions. The present paper summarises the results of the assessment and evaluation of models for predicting the behaviour of radionuclides in lacustrine ecosystems. Such models were developed and tested within major projects financed by the European Commission during its 4th Framework Programme (1994-1998). The work done during the recent decades by many modellers at an international level has produced some consolidated results that are widely accepted by most experts. Nevertheless, some new results have arisen from recent studies and certain model improvements are still necessary.     

Availability of 99Tc in undisturbed soil cores

Models for safety assessment of radioactive waste repositories need accurate values of the soil-to-plant transfer of radionuclides. In oxidizing environments, (99)Tc is expected to occur as pertechnetate ((99)TcO(4)(-)). Due to its high mobility, leaching of this element in the field might be important, potentially affecting the reliability of estimated transfer parameters of (99)Tc as measured in closed experimental systems such as hydroponics or pot experiments. The aim of this experiment was to measure the leaching of (99)Tc in undisturbed irrigated soil cores under cultivation as well as plant uptake and to study the possible competition between the two transfer pathways. Undisturbed soil cores (50 x 50 cm) were sampled from a Rendzic Leptosol (R), a colluvial Fluvic Cambisol (F) and a Dystric Cambisol (D) using PVC tubes (three cores sampled per soil type). Each core was equipped with a leachate collector at the bottom, allowing the monitoring of (99)Tc leaching through the cores. Cores were placed in a greenhouse and maize (Zea mays L., cv. DEA, Pioneer) was sown. After 135 d, maize was harvested and radioactivity determined in both plant and water samples. Results showed that during the growing period, leaching of (99)Tc was limited, due to the high evapotranspiration rate of maize. After harvest, leaching of (99)Tc went on because of the absence of evapotranspiration. Effective uptake (EU) of (99)Tc in leaves and grains was calculated. EU reached 70% of the input in the leaves and was not significantly different among soils. These results confirmed those obtained from pot experiments, even though leaching was allowed to occur in close-to-reality hydraulical conditions. As a consequence, it was concluded that pot experiments are an adequate surrogate for more complex "close-to-reality" experimental systems for measuring transfer factors.