Imazaquin adsorbed on pillared clay and crystal violet-montmorillonite complexes for reduced leaching in soil

Ground water pollution due to herbicide leaching has become a serious environmental problem. Imazaquin [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid] is an herbicide used to control broadleaf weeds in legume crops. Imazaquin is negatively charged at the basic pH of calcareous soils and exhibits high leaching potential in soils. Our aim was to design formulation of imazaquin to reduce herbicide leaching. Imazaquin sorption on pillared clay (PC) and crystal violet (CV)-montmorillonite complexes was studied. The CV-montmorillonite complexes become positively charged with adsorption of CV above the cation exchange capacity (CEC) of montmorillonite, and thus can sorb imazaquin. The Langmuir equation provides a good fit to isotherms of imazaquin sorption on PC and CV-montmorillonite complexes, but for charged complexes an equation that combines electrostatics with specific binding was preferred. Maximal imazaquin sorption was 17.3 mmol kg-1 for PC and 22.2 mmol kg-1 for CV-montmorillonite complexes. The extents of imazaquin desorption into water were 21% for PC and 5% for CV-clay complexes. The presence of anions decreased imazaquin sorption on both sorbents in the sequence phosphate > acetate > sulfate. Reduction of imazaquin sorption by the anions and the extent of its desorption in electrolyte solutions were higher for PC than for CV-clay complexes. Leaching of imazaquin from CV-montmorillonite formulations through soil (Rhodoxeralf) columns was two times less than from PC formulations and four times less than that of technical imazaquin. The CV-montmorillonite complexes at a loading above the CEC appear to be suitable for preparation of organo-clay-imazaquin formulations that may reduce herbicide leaching significantly.     

Speciations of trace metals in the Danube alluvial sediments within an oil refinery

A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.     

Sexual and asexual reproduction of<Emphasis Type="Italic"> Allostichaster capensis</Emphasis> (Echinodermata: Asteroidea) in Golfo Nuevo

Sexual and asexual reproduction of the fissiparous starfish Allostichaster capensis were examined for 24 months at Bahía Kaiser, Golfo Nuevo, Chubut, Argentina. Gonad indices revealed an annual reproductive cycle, with peak development occurring in late winter (August). Spawning occurred in spring (September). Pyloric caeca indices displayed a clear annual cycle and a reciprocal relationship with gonad indices, showing the storage function of pyloric caeca. The starfish population appears to be largely maintained by fission, as only two females were found. A. capensis also showed an annual cycle of fission, with the highest frequency in spring and summer (from November to January), just after spawning. Incidence of fission was correlated with environmental factors such as photoperiod, seawater temperature, and salinity.Communicated by P.W. Sammarco, Chauvin     

Reproductive biology of <Emphasis Type="Italic">Cosmasterias lurida</Emphasis> (Echinodermata: Asteroidea) an anthropogenically influenced substratum from Golfo Nuevo,Northern Patagonia (Argentina)

The starfish Cosmasterias lurida was sampled from the pier piles of Almirante Storni in the Golfo Nuevo, northern Patagonia, from November 2001 to November 2003. In this anthropogenically modified site there is an unusually abundant food supply of mussels and large aggregations of starfishes. The reproductive cycle was studied by organ indices and histological examination of gonads. The highest gonad index (GI) values were found in the summer (February–March), followed by a drop in GI values, indicating spawning. Histological analyses indicated that gametogenesis takes place from June to January, sexual maturity occurred during the summer and spawning occurred in April. The GI and pyloric caeca index (PCI) tended to have an inverse relationship, but this was only statistically significant in males. However, biochemical analyses of the starfish indicated no transfer of nutrients between pyloric caeca and gonads in either sex. In fact, simultaneous accumulation of carbohydrates was found in the pyloric caeca and gonads of both sexes.     

Design and field application of an automated cartridge sampler for VOC concentration and flux measurements

One of the major limitations in advancing the understanding of tropospheric ozone and aerosol generation and developing strategies for their control is the technical ability to accurately measure volatile organic compounds (VOCs). This paper describes the design of a constant flow VOC sampler. The versatile sampler can be used for fully automated concentration and flux measurements of VOCs. The sampler incorporates a microprocessor control unit and provides highly accurate mass flow control and significant ease of operation. Sampling sequences can be programmed directly or by remote control through a PC. All important operational parameters necessary for a complete sampling audit trail are logged. Compact weatherproof housings and low power consumption allow operation at remote sites and locations which are sensitive to disturbances or have restricted access. Inner wetted surfaces of the sampler are constructed from non-contaminating materials that do not sorb or emit VOC, and thus permit the collection of representative samples even in environments with very low VOC concentrations. The cartridge magazine provides a maximum of 20 sequential cartridge samples, which allows for long-term air quality assessments. In the dual channel mode, two samples can be collected simultaneously through two independent sample loops, providing ten sequential sample pairs. This design allows the parallel collection of (a) quality assurance backup samples, (b) samples on two different types of cartridges/sorbents to allow a variety of analyses, or (c) differential samples for flux measurements using enclosure, aerodynamic profile, or relaxed eddy accumulation (REA) methods. Field applications including airplane profile measurements above a tropical rainforest area, as well as gradient and REA measurements over a mid-latitude mixed forest stand are described, and demonstrate the validity and flexibility of the system. In particular, the application of the VOC sampler as an integrated part of a REA system is emphasized.     

δ<Superscript>13</Superscript>C and δ<Superscript>15</Superscript>N values in reef corals <Emphasis Type="Italic">Porites lutea</Emphasis> and <Emphasis Type="Italic">P. cylindrica</Emphasis> and in their epilithic and endolithic algae

In summer 1998, shallow water corals at Sesoko Island, Japan (26°38′N, 127°52′E) were damaged by bleaching. In August 2003, partially damaged colonies of the massive Porites lutea and the branching P. cylindrica were collected at depths of 1.0–2.5 m. The species composition of epilithic algal communities on dead skeletal surfaces of the colonies (‘red turfs’, ‘green turfs’, ‘red crusts’) and the endolithic algae (living in coral skeletons) growing close to and away from living coral polyps was determined. Carbon and nitrogen stable isotope values of organic matter (δ¹³C and δ¹⁵N) from all six of these biological entities were determined. There were no significant differences in the isotope composition of coral tissues of the two corals, with P. lutea having δ¹³C of −15.3 to −9.6‰ and δ¹⁵N of 4.7–6.1‰ and P. cylindrica having similar values. Polyps in both species living close to an interface with epilithic algae had similar isotope values to polyps distant from such an interface. Despite differences in the relative abundance of the algal species in red turfs and crusts, their δ¹³C and δ¹⁵N values were not significantly different from each other (−18.2 to −13.9, −20.6 to −16.2, 1.1–4.3, and 3.3 to 4.9‰, respectively). The green algal turf had significantly higher δ¹³C values (−14.9 to −9.3‰) than that of red turfs and crusts but similar δ¹⁵N (1.2–4.1‰) to the red algae. The data do not suggest that adjoining associations of epilithic algae and coral polyps exchange carbon- and nitrogen-containing metabolites to a significant extent. The endolithic algae in the coral skeletons had δ¹³C values of −14.8 to −12.3‰ and δ¹⁵N of 4.0–5.4‰. Thus they did not differ significantly from the coral polyps in their carbon and nitrogen isotope values. The similarity in carbon isotope values between the coral polyps and endolithic algae may be attributed to a common source of CO₂ for zooxanthellae and endolithic algae, namely, from respiration by the coral host. While it is difficult to fully interpret similarity in the nitrogen isotope composition of coral tissue and of green endolithic algae and the difference in δ¹⁵N between green epilithic and endolithic algae, the data are consistent with nitrogen-containing metabolites from the scleractinian coral serving as a significant source of nitrogen for the endolithic algae.     

Source apportionment of polycyclic aromatic hydrocarbons in Lake Baikal water and adjacent air layer

The composition of polycyclic aromatic hydrocarbons (PAHs) in Lake Baikal water and adjacent air layer and PAH emission composition profiles of possible sources were investigated. Analysis of emission composition data showed that the source profiles could not be grouped by fuel type or pyrogenic/petrogenic origin. Because of the similarity of source PAH profiles, the drawing of 3D mixing diagrams was the only way to check whether some of the potential PAH sources were the true sources. The mixing diagrams showed that the sources of air pollution were paper mills and wood burning and that the sources of water pollution were coal-fired and oil-fired boilers. The common source for both air and water was only oil and petroleum products. To determine the locations of PAH sources, their contributions to air and water pollution were calculated and mapped. Based on the results, air and water were polluted from both local and regional sources. The location of the zone influenced by a particular source was conditioned by physical properties of source emission, direction of air/water flows that transfer PAHs and temperature differences between mixing air/water flows.     

Calcite precipitates in Slovenian bottled waters

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg²⁺, SO₄ ²⁻, SiO₂, Al, Mn and other impurities such as K⁺, Na⁺, Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.