A new method for the determination of trichloroacetic acid in spruce foliage and other environmental media

Trichloroacetic acid (TCAA) is a phytotoxic chemical, present throughout the environment. The majority of methods for analysis of TCAA require chemical derivatisation and multiple extraction steps prior to analysis by gas-chromatography. Here, a new analytical method for TCAA determination in environmental matrices is reported. The method is based on a modified Nielsen-Kryger steam distillation that combines into one 1 h reflux the thermal decarboxylation of TCAA to CHCl3 and the partitioning and concentration of the CHCl3 into 5 ml of hexane, which is analysed by GC. Sample preparation is minimal and no matrix standard additions are required. The background CHCl3 in the sample is removed prior to extraction by degassing the solution for 1 h with nitrogen. Optimisation of the method gave recoveries from three separate solutions of 0.31 ppb aqueous TCAA standards of 93 +/- 15% (n = 9), 110 +/- 9% (n = 9) and 105 +/- 11% (n = 6). The extraction method has been compared with a decarboxylation and headspace GC method for determination of TCAA in Sitka spruce needles. No significant difference in TCAA concentration or replicate precision between the two methods was observed.     

Intrasite sampling of Hong Kong soils contaminated by Caesium-137

Previous measurements of soil contamination by Caesium-137 (137Cs) in Hong Kong have been used both to estimate background levels prior to the construction of the Guangdong Nuclear Power Station (GNPS) at Daya Bay and to evaluate health hazards arising from the radionuclide. These measurements are reviewed and contrasted with recent advances in understanding of 137Cs distribution in soil. Preliminary research findings are used to illustrate the microscale variability of 137Cs in the Hong Kong environment and to suggest intrasite sampling methods for establishing suitable reference values.     

Plant origin of Okinawan propolis: honeybee behavior observation and phytochemical analysis

Propolis is a natural resinous product collected by honeybees from certain plants. It has gained popularity as a food and alternative medicine. Poplar and Baccharis are well known as the source plants of European and Brazilian propolis, respectively. However, the propolis from Okinawa, Japan, contains some prenylflavonoids not seen in other regions such as Europe and Brazil, suggesting that the plant origin of Okinawan propolis is a particular plant that grows in Okinawa. To identify the plant origin of Okinawan propolis, we observed the behavior of honeybees as they collected material from plants and caulked it inside the hive. Honeybees scraped resinous material from the surface of plant fruits of Macaranga tanarius and brought it back to their hive to use it as propolis. We collected samples of the plant and propolis, and compared their constituents by high-performance liquid chromatography with a photo-diode array detector. We also compared their 1,1-diphenyl-2-picryl-hydrazyl radical scavenging activity. The chemical constituents and biological activity of the ethanol extracts of the plant did not differ from those of propolis. This indicates directly that the plant origin of Okinawan propolis is M. tanarius. S. K. and J. N. contributed equally to this work.     

Glutathione S-transferase cytosolic isoform in the pink-shrimp, Farfantepenaeus brasiliensis, from Conceição Lagoon, Santa Catarina Island, SC, Brazil

Contaminant input into the environment can affect the biochemical responses of exposed organisms. Activity of conjugation enzymes, such as glutathione S-transferase (GST) has been proposed as a biomarker of susceptibility to the presence of potentially damaging xenobiotics. The aim of the present study was to evaluate the activity of total and Pi-class GST in the hepatopancreas of pink-shrimp Farfantepenaeus brasiliensis. The shrimp were caught at a single site at Concei??o Lagoon and transplanted to another site (Canto da Lagoa - CA) in the same lagoon, and to the laboratory (LAB), where they were kept for 15 days. This experiment was carried out in winter 2003 and in summer 2004. Shrimp were sampled before the exposure, at a zero time (t0), and after 15-days at CA site and LAB. The activity of total GST and Pi-isoform were analyzed using CDNB and ethacrynic acid (EA) as substrates, respectively. Shrimp caught in winter showed higher levels of Pi-class GST than those caught in summer, for both t0 and CA groups. Moreover, differences in the activity of this GST isoform between groups were observed only in winter, where the animals from t0 and CA groups presented higher activity when compared to those kept in the laboratory. This difference could be associated either to changes in the contaminant input or to other water quality parameters in this ecosystem. The elevated GST Pi activity observed in the shrimp of both t0 and CA groups sampled in winter could be related to salinity, since it was higher in winter than in summer. We could also suggest a possible association of this finding to a seasonal metabolic variation in this penaeid. If that is the case, one should take into account these alterations when considering the use of this GST isoform as biomarker in F. brasiliensis in environmental monitoring programs.     

Pollution profiles and physicochemical parameters in old uncontrolled landfills

The long-term effectiveness of the geological barrier beneath municipal-waste landfills is a critical issue for soil and groundwater protection. This study examines natural clayey soils directly in contact with the waste deposited in three landfills over 12 years old in Spain. Several physicochemical and geological parameters were measured as a function of depth. Electrical conductivity (EC), water-soluble organic carbon (WSOC), Cl⁻, NH₄⁺, Na⁺ and exchangeable NH₄⁺ and Na⁺ were used as parameters to measure the penetration of landfill leachate pollution. Mineralogy, specific surface area and cationic-exchange capacities were analyzed to characterize the materials under the landfills. A principal component analysis, combined with a Varimax rotation, was applied to the data to determine patterns of association between samples and variables not evident upon initial inspection. The main factors explaining the variation in the data are related to waste composition and local geology. Although leachates have been in contact with clays for long time periods (13-24 years), WSOC and EC fronts are attenuated at depths of 0.2-1.5 m within the clay layer. Taking into account this depth of the clayey materials, these natural substrata (>45% illite-smectite-type sheet silicates) are suitable for confining leachate pollution and for complying with European legislation. This paper outlines the relevant differences in the clayey materials of the three landfills in which a diffusive flux attenuation capacity (A_c) is defined as a function (1) of the rate of decrease of the parameters per meter of material, (2) of the age and area of the landfill and (3) of the quantity and quality of the wastes.     

Formation of nitrogenous disinfection by-products from pre-chloramination

A sampling survey investigated the formation of nitrogenous disinfection by-products (N-DBPs) and carbonaceous DBPs (C-DBPs) from pre-chloramination, an increasingly common treatment strategy in China for regulated C-DBP control, followed by subsequent conventional water treatment processes, i.e., coagulation, sedimentation, and filtration. Dihalogenated N-DBPs typically peaked in the summer and early autumn with a relatively higher temperature, with the maximum levels of dichloroacetamide (DCAcAm), dichloroacetonitrile (DCAN), bromochloroacetonitrile, dibromoacetonitrile and dichloroacetone at 1.8, 6.3, 6.0, 2.6 and 1.8 μg L⁻¹ in the finished water, respectively. Also, the levels of all the dichlorinated N-DBPs were correlated with the ratio of dissolved organic nitrogen (DON) to dissolved organic carbon, implying autochthonous DON played an essential role in the formation of these DBPs. In contrast, the yields of trihalogenated DBPs [chloroform (CF), trichloronitromethane (TCNM) and trichloroacetone (TCAce)] appeared not to be significantly affected by seasons. CF and DCAN were the dominant species in trihalomethanes (THMs) and dihaloacetonitriles (DHANs), respectively. Bromine was more readily incorporated into DHANs to form brominated DBPs than THMs during pre-chloramination. Although pre-chloramination can ensure the finished water to meet with the current Chinese THM regulatory limits, the increased levels of TCNM and TCAce may be a new water quality concern.     

Photodegradation of Diquat and Paraquat in aqueous solutions by titanium dioxide: evolution of degradation reactions and characterisation of intermediates

The titanium dioxide assisted photodegradation of Diquat and Paraquat herbicides solutions has been the subject of the present investigation, considering its direct application in the treatment of contaminated waters and soils. To have a better understanding of the photodegradation process, different types of TiO2, commercial and 'home prepared' Ti(1-x)FexO2 (x = 0% and 4%), were used as catalysts, using an UV light as radiation source. The degradation reactions were followed by UV spectroscopy and the intermediates and reaction products were characterised by electrospray ionisation mass spectrometry (ESIMS) combined with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS). The present study shows that, for photocatalytic degradation of Diquat and Paraquat solutions, a basic pH can be determinant, as well as the type of catalyst. The type of catalyst can also strongly influence the degradation pattern of the herbicide. Regarding complete degradation, we were able to show that Diquat is more persistent than Paraquat. During the photocatalytic processes, several intermediate and reaction products are sequentially formed, to which structures are proposed.