On the thermally induced isomerisation of hexabromocyclododecane stereoisomers

The interconversion of the stereoisomers contained in technical 1,2,5,6,9,10-hexabromocyclododecane, a major brominated flame retardant increasingly found in the environment and in biota, was investigated at elevated temperatures. The application of pure enantiomers of the three constituents alpha-, beta-, and gamma-HBCD enabled the unambiguous elucidation of the individual isomerisation reactions as well as the quantification of all respective rate constants. At 160 degrees C the rate constants range over two orders of magnitude from 1.50x10(-3) to 1.88x10(-5)mol(%)s(-1). A preliminary mechanistic explanation for the differences of the rate constants which govern the composition of HBCD diastereomers at equilibrium is given.     

Fate and degradation of the chemical warfare agent soman on sands

Soman is one of the most toxic nerve agents of the known chemical warfare agents. There is actually few knowledge on the behavior of soman in the event of an environmental contamination. It is in particular unknown whether soman remains on a given surface, evaporates into air, or degrades. Here, we studied the evaporation of soman deposited on silica sand using a laboratory-sized wind tunnel, thermal desorption, and gas chromatography. We also investigated the degradation of soman on silica sand by ³¹phosphorus solid state magic angle spinning nuclear magnetic resonance and gas chromatography–mass spectrometry. Results show that a drop of soman on silica sand spreads laterally while evaporating. The maximum vapor concentration was found when the spreading of the soman drop was maximum on the surface. Simultaneously, soman was absorbed gradually into the pore of sand and degraded to O-pinacolyl-methylphosphonic acid following a pseudo-first-order rate reaction over weeks. To our best knowledge, this is the first report on the fate of soman in a sandy environment.     

Terpenoids tame aggressors: role of chemicals in stingless bee communal nesting

Social insects aggressively defend their nest and surrounding against non-nestmates, which they recognize by an unfamiliar profile of aliphatic hydrocarbons on the cuticle. Prominent exceptions are communal nest aggregations of stingless bees. Stingless bees (Apidae: Meliponini) are also unique in possessing cuticular terpenes which are derived from tree resins and have not yet been reported for any other insect. We showed experimentally that sesquiterpenes from the body surface of the communal nesting bee Tetragonilla collina reduced aggression in otherwise aggressive bees which did not have sesquiterpenes themselves. In the field, bee species nesting in aggregations with T. collina often lack sesquiterpenes in their own cuticular profiles. These species show little aggression towards T. collina, whereas it can be heavily attacked by non-aggregated species that also possess cuticular sesquiterpenes. We conclude that appeasement by sesquiterpenes represents a novel mechanism to achieve interspecific tolerance in social insects.     

Numerical and field investigation of enhanced in situ denitrification in a shallow-zone well-to-well recirculation system

This study investigated efficiency of in situ enhanced biological denitrification of nitrate-contaminated groundwater which employs a well-to-well circulation in a shallow zone where oxygen might give an adverse affect on the denitrification processes. The numerical model developed for the efficiency test included sequential aerobic and nitrate-based respiration, multi-Monod kinetics of reactive components, growth and decay of biomass, and denitrification inhibition associated with the presence of oxygen. Moreover, reaction kinetics for production of toxic intermediates such as nitrite and nitrous oxide were also included in the model. The developed model was applied to the analysis of enhanced in situ denitrification using an injection/extraction well pair. To evaluate the relative remediation effectiveness, comparisons were made between a continuous fumarate injection test (CFIT) system and a pulsed fumarate injection test (PFIT) system, where both systems had the same total fumarate mass injected into the aquifer. The PFIT system was preferable to the CFIT system because of the high possibility of occurrence of clogging in the latter case at the injection well, with no other significant advantages found in either the CFIT or the PFIT system. Accordingly, this developed numerical model is useful to predict and evaluate an in situ bioremediation by denitrification in aquifers.     

Optical and microphysical properties of severe haze and smoke aerosol measured by integrated remote sensing techniques in Gwangju,Korea

Aerosol optical and microphysical parameters from severe haze events observed in October 2005 at Gwangju, Korea (35.10°N, 126.53°E) were determined from the ground using a multi-wavelength Raman lidar, a sunphotometer, and a real-time carbon particle analyzer and from space using satellite retrievals. Two different aerosol types were identified based on the variability of optical characteristics for different air mass conditions. Retrievals of microphysical properties of the haze from the Raman lidar indicated distinct light-absorbing characteristics for different haze aerosols originating from eastern and northern China (haze) and eastern Siberia (forest-fire smoke). The haze transported from the west showed moderately higher absorbing characteristics (SSA = 0.90 ± 0.03, 532 nm) than from the northern direction (SSA = 0.96 ± 0.02). The organic/elemental carbon (OC/EC) ratio varied between 2.5 ± 0.4 and 4.1 ± 0.7.     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Seasonal Variations and Chemical Forms of Heavy Metals in Soils and Dusts from the Satellite Cities of Seoul, Korea

This research investigated heavy metal pollution of soils and dusts in two representative satellite cities of Seoul, Korea and studied the seasonal variations in metal concentrations through the rainy season and the chemical forms of metals using a sequential extraction analysis. The metal dispersion pattern was illustrated to match with urban structure. Soil and dust samples were collected from the cities of Uijeongbu and Koyang, which are the northern and northwestern satellite cities of Seoul (the capital), before and after rainy season. Concentrations of Cu, Pb and Zn were higher than those of the world averages for soils, and their levels decreased after rain, particularly in highly contaminated samples. Relatively high pH values were found in roadside soils, but no seasonal variation was found after the rainy season. The three metals (Cu, Pb and Zn) in soils and dusts were associated with various chemical fractions of soils and dusts as distinguished by the sequential extraction scheme, and a strong similarity of metal association between soils and dusts was found, which indicates that airborne dust may be a principle source of soil contamination. Copper is uniformly distributed, and Pb is largely associated with the reducible phase. There is an appreciable proportion of total Zn in the exchangeable/water-acid soluble fraction. After the rainy season, the most soluble fractions in soils and dusts were leached away. In terms of mobility and bioavailability of metals in soils and dusts, the order Zn >> Cu > Pb is suggested. Geographical variations of total metals corresponded well with urbanised areas of cities, especially the industrial complex and major motorways.     

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Phosphate removal and recovery with a synthetic hydrotalcite as an adsorbent

Phosphate removal is important to control eutrophication and an ion exchange process is one of several treatment processes for this purpose. Hydrotalcite compounds (HTALs) are useful as adsorbents for phosphate removal because of their ion exchange properties. In this study, the adsorption properties of a granular synthetic HTAL for phosphate and the method of regeneration of the granular HTAL were examined. The adsorption isotherm of the granular HTAL was approximated by a modified Langmuir type, and the maximum adsorption capacity was 47.3 mg P g(-1), which corresponded to the content of HTAL in the granular one. Phosphate adsorbed on the HTAL was effectively desorbed with alkaline NaCl solutions and the HTAL was regenerated with 25 w/v% MgCl(2) solution. The regenerated HTAL could be reused repeatedly for the phosphate removal. Phosphate in the exhausted desorption solution was recovered as a precipitate of calcium phosphate by addition of CaCl(2), and the residual exhausted desorption solution could be also reused after supplying NaOH. The results suggest the possibility of an effective system for phosphate removal and recovery, which includes the following processes: adsorption, desorption, recovery of phosphate, and regeneration of the HTAL and the desorption solution.