New procedures for simultaneous determination of mesotrione and atrazine in water and soil. Comparison of the degradation processes of mesotrione and atrazine

A method for the determination of residues of mesotrione, atrazine and its degradation products: deethylatrazine, hydroxyatrazine, deisopropylatrazine, desethyldesisopropylatrazine in a variety of water and soil matrices has been developed. Mesotrione is a new selective herbicide for use in corn, which has been substituted for atrazine, which has been banned in European Union countries since 2007. Although atrazine has not been used for three vegetative periods, it is still detected in the environment. The analysis was conducted by means of ultra-high-pressure liquid chromatography with ultraviolet detection and liquid chromatography with diode array detection. The procedures for analyte separation from water and soil matrices were also established. The optimal conditions for solid-phase extraction (SPE) were determined. The recoveries were compared with that obtained by means of SPE. Method fortification recoveries from water samples averaged 78–97% and for soil 80–97% depending on the analyte and type of sample. The limits of detection were 0.04–0.61 μg/L for water samples and for soil samples 0.02–0.88 μg/g. The soil samples were collected in spring 2009 from three different fields with water samples being made from effluents from these fields. Samples collection was conducted in the day of mesotrione (Callisto 100SC) application and then done weekly, until the mesotrione concentration was below the limit of quantification. The results enabled the monitoring of mesotrione degradation in soil and its permeability into surface waters; simultaneously, the same studies were conducted for atrazine.     

Atmospheric background trace elements deposition in Tierra del Fuego region (Patagonia,Argentina), using transplanted <Emphasis Type="Italic">Usnea barbata</Emphasis> lichens

Lichen, Usnea barbata, transplants taken from Tierra del Fuego (south Patagonia, Argentina) were tested as potential biomonitors of atmospheric airborne deposition in an apparently pristine environment. In 2005, lichens were sampled in a reference site (n = 31) and transplanted in the northern Region of Tierra del Fuego. After, respectively, 1 month and 1 year of exposure, we collected them. The aim of the study was to determine the bioaccumulation of 26 elements in order to evaluate the background levels in the selected area. Samples were analyzed by the sector field inductively coupled plasma mass spectrometry. Discriminant analysis on principal component analysis factors was applied in order to explore the relationship among the different elements as far as time and spatial variation in transplants regards. The analysis was tested by Monte Carlo test based on 999 replicates. The most important contamination source resulted to be the atmospheric soil particle deposition. Furthermore, the results were compared with those obtained from the lichens collected in central and southern Tierra del Fuego. This study confirms the ability of U. barbata to reflect the background levels of the 26 elements in that environment. Compared with other background sites in the world, we did confirm that Tierra del Fuego lichens have a low content of the studied elements. Tierra del Fuego turned out not to be a pristine environment as supposed, but it can be considered as a reference basal ecosystem for useful comparisons among different geographical areas. These findings can be very relevant and useful for environmental conservation programs.     

Occurrence of diarrhetic shellfish poisoning (DSP) toxins in clams (Ruditapes decussatus) from Tunis north lagoon

The main diarrhetic shellfish toxins, okadaic acid (OA) and dinophysistoxin-1, 2 (DTX-2, 2) were detected by liquid chromatography-tandem mass spectrometry (LC-MS/MS) as pyrenacyl esters in clams (Ruditapes decussatus) collected in Tunis north lagoon from January 2007 to June 2008. Sample analyses by LC-MS/MS displayed OA and related congeners (DTX-2, 2) with a highest detected level of 21 μg OA eq/kg shellfish meat for the samples of January 2007. Nevertheless, all samples were MBA negative. During the study period, potentially toxic dinoflagellate Dinophysis sacculus was recorded all year, blooming at different times. Highest concentrations were recorded during January 2007 with 4.6?×?10(4) cells per liter and 4.10(4) cells per liter in the northern and southern districts, respectively. Results show that there is no significant correlation between D. sacculus densities in water column and diarrhetic shellfish poisoning (DSP) toxins concentrations unregistered in clams. These data reveal that DSP toxicity in clams of Tunis north lagoon is low according to European regulatory limit (160 μg OA eq/kg shellfish meat). However, a potential threat, in this area, is represented by DSP toxic species as D. sacculus and provides grounds for widen and reinforcing sanitary control of the phycotoxin measures in the region.     

Chemical composition of ambient particulate matter and redox activity

Exposure to ambient particulate matter (PM) has been associated with a number of adverse health effects. Increasing studies have suggested that such adverse health effects may derive from oxidative stress, initiated by the formation of reactive oxygen species (ROS) within affected cells. The study aimed to assess physical characteristics and chemical compositions of PM and to correlate the results to their redox activity. PM_2.5 (mass aerodynamic diameter ≤2.5 μm) and ultrafine particles (UFPs, mass media aerodynamic diameter <0.1 μm) were collected in an urban area, which had heavy traffic and represented ambient air pollution associated with vehicle exhaust. Background samples were collected in a rural area, with low traffic flow. Organic carbon (OC), elemental carbon (EC), polycyclic aromatic hydrocarbons (PAHs), and metals were analyzed. The dithiothreitol activity assay was used to measure the redox activity of PM. Results showed that UFPs have higher concentrations of OC, EC, and PAHs than those of PM_2.5. Several metals, including Fe, Cu, Zn, Ti, Pb, and Mn, were detected. Among them, Cu had the highest concentrations, followed by Fe and Zn. Organic carbon constituted 22.8% to 59.7% of the content on the surface of PM_2.5 and UFPs. Our results showed higher redox activity on a per PM mass basis for UFPs as compared to PM_2.5. Linear multivariable regression analyses showed that redox activity highly correlated with PAH concentrations and organic compounds, and insignificantly correlated with EC and metals, except soluble Fe, which increased redox activity in particle suspension due to the presence of ROS.     

The physico-chemical properties and leaching behaviors of phosphatic clay for immobilizing heavy metals

In this study, phosphatic clay was used as a phosphate containing material. The fractionation of phosphorus was carried out using the CRM BCR-684 protocol, and the inorganic phosphorus, especially all the apatite phosphorus, was found as the major form. The elemental compositions of the phosphatic clay were identified using an X-ray fluorescence spectrometer, and was found to be mainly composed of CaO and P2O5. The specific surface area, pore volume and average pore diameter were measured also. Results of experiment show that the phosphatic clay may provide a cost-effective way to remediate heavy metal contaminated aqueous and slurry phase.     

Environmental management aspects for TBT antifouling wastes from the shipyards

Tributyltin (TBT)-based antifouling paints have been successfully used for over 40 years to protect a ship's hull from biofouling. However, due to its high toxicity to marine organisms, the International Maritime Organization (IMO), in 1990, adopted a resolution recommending governments to adopt measures to eliminate antifouling paints containing TBT. High concentrations of TBT are detected in the vicinity of ports and shipyards. TBT is also usually detected in the sediment, in which it accumulates. This study reviews recent literature for the best management practices (BMPs) in order to minimize the environmental effects of TBT. The paper focuses on the evaluation of the available techniques for the removal of TBT from shipyard wastes and from the sediment. The most effective treatment methods are highlighted. BMPs include recycling of abrasive materials, use of cleaner abrasive materials, reuse of spent abrasive materials, substitution of hydroblasting by vacuum blasting or containment or ultra-high-pressure water blasting and confinement of pollution by enclosure and containment systems. The treatment of the TBT wastes by conventional biological wastewater treatment processes is probably not suitable, because the concentrations of TBT found in shipyards' wastewaters are toxic to microorganisms. Advanced technologies such as activated carbon adsorption and dissolved air flotation, in combination with filtration and coagulation-clarification, photodegradation and electrochemical treatment, are required to remove TBT. However, advanced methods should be further optimized to meet the regulatory limit of 200 ng/L. To date, only one published work examines the efficiency of incineration for the treatment of solid sandblast wastes. Regarding the treatment of sediment, land deposition of the less polluted fraction of sediment is a feasible option. Such treatment must take into account the risk of contamination of groundwater and the surroundings, and it requires extended areas of land. Other treatment methods, such as thermal and electrochemical treatment, are promising options but due to the large amounts of dredged material, they have high capital and operational costs.     

Climate Change Adaptation for the US National Wildlife Refuge System

Since its establishment in 1903, the National Wildlife Refuge System (NWRS) has grown to 635 units and 37 Wetland Management Districts in the United States and its territories. These units provide the seasonal habitats necessary for migratory waterfowl and other species to complete their annual life cycles. Habitat conversion and fragmentation, invasive species, pollution, and competition for water have stressed refuges for decades, but the interaction of climate change with these stressors presents the most recent, pervasive, and complex conservation challenge to the NWRS. Geographic isolation and small unit size compound the challenges of climate change, but a combined emphasis on species that refuges were established to conserve and on maintaining biological integrity, diversity, and environmental health provides the NWRS with substantial latitude to respond. Individual symptoms of climate change can be addressed at the refuge level, but the strategic response requires system-wide planning. A dynamic vision of the NWRS in a changing climate, an explicit national strategic plan to implement that vision, and an assessment of representation, redundancy, size, and total number of units in relation to conservation targets are the first steps toward adaptation. This adaptation must begin immediately and be built on more closely integrated research and management. Rigorous projections of possible futures are required to facilitate adaptation to change. Furthermore, the effective conservation footprint of the NWRS must be increased through land acquisition, creative partnerships, and educational programs in order for the NWRS to meet its legal mandate to maintain the biological integrity, diversity, and environmental health of the system and the species and ecosystems that it supports.     

Biodegradation and sorption of nodularin (NOD) in fine-grained sediments

Nodularin (NOD) is a cyclic pentapeptide hepatotoxin produced by the bloom forming cyanobacterium Nodularia spumigena. The fate of the toxin in the aquatic environment has not been fully evaluated. In the current study the changes in NOD concentration caused by biodegradation and sorption in samples from the Baltic were studied. Seawater of various salinities (0, 4, 8 and 12 PSU) and three forms of fine-grained sediment (sterile wet sediment, non-sterile wet sediment, and combusted sterile sediment) were incubated with 34.7 μg of NOD. The toxin was seen to be highly stable both in sterile and non-sterile seawater. During the 21-day experiment NOD concentrations in solutions overlying the combusted sediment and the sterile wet sediment were reduced to 12.5 ± 2.6% and 59.8 ± 2.4% of the initial value. The greatest loss of the toxin (up to 100%) was observed in the non-sterile seawater incubated with non-sterile wet sediment. These results indicate an important role of benthic microbial community in nodularin removal. Two biodegradation products with similar spectral characteristics to NOD were detected; one of which was identified as Adda amino acid.     

Riboflavin content of coelomocytes in earthworm (Dendrodrilus rubidus) field populations as a molecular biomarker of soil metal pollution

The effect of Pb + Zn on coelomocyte riboflavin content in the epigeic earthworm Dendrodrilus rubidus inhabiting three metalliferous soils and one reference soil was measured by flow cytometry and spectrofluorimetry. A reciprocal polluted↔unpolluted worm transfer experiment (4-week exposure) was also performed. High proportions of autofluorescent eleocytes were counted in worms from all localities, but intense riboflavin-derived autofluorescence was detectable only in reference worm eleocytes. Other findings were: (i) fluorophore(s) other than riboflavin is/are responsible for eleocyte autofluorescence in residents of metalliferous soils; (ii) riboflavin content was reduced in the eleocytes of worms transferred from unpolluted to metal-polluted soil; (iii) the riboflavin content of D. rubidus eleocytes is a promising biomarker of exposure; (iv) COII mitochondrial genotyping revealed that the reference population is genetically distinct from the three mine populations; (v) metal exposure rather than genotype is probably the main determinant of inter-population differences in eleocyte riboflavin status.