Remediation of soil contaminated with dioxins by subcritical water extraction

The effectiveness of subcritical water extraction (SCWE) was examined for removing dioxins from contaminated soil. Most dioxins in the soil sample were reduced at 300 degrees C or more, but decreased dioxin concentrations were also observed at 150 degrees C. After 4 h of extraction, 99.4%, 94.5% and 60% of PCDDs were removed from samples at 350, 300 and 150 degrees C, respectively. It was also determined that degradation of dioxins had occurred, since the sum of dioxins in the soil plus water extracts after the experiments had considerably decreased. This study revealed that pressurizing is not essential for the removal of dioxins. Reduction was complete within 30 min at 350 degrees C; however, it took a much longer time at lower temperatures. The results of addition experiments in which OCDDs were added to different types of soil samples have shown that dechlorination is one of the major reaction pathways. After addition of OCDD to soil samples, experiments were carried out to examine in detail the degradation pathways of PCDDs. The removal rates and congener profiles varied among soil types. Although it was previously assumed that removal rates and congener profiles depended on the chemical components in soil, nonparametric statistical analysis revealed no significant relationship between the rate of reduction and elements present in the soil. It was confirmed from isomer patterns that dechlorination of the 2,3,7,8-positions in PCDDs takes place somewhat faster than for the 1,4,6,9-positions.     

Modified clean-up for PBDD,PBDF and PBDE with an active carbon column--its application to sediments

A clean-up method for polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples.     

Elemental composition of a tusk of a dugong, Dugong dugon, from Exmouth, Western Australia

Element analysis of the annual increments in a longitudinal section from the tusk of a female dugong Dugong dugon (Müller) from Exmouth, Western Australia, was carried out by X-ray fluorescence-imaging, inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS). Nine elements (Ba, Ca, Fe, Li, Mg, Na, P, Sr and Zn) were present in concentrations amenable to determination by these techniques. Most elements revealed both long-term trends and shorter, year-to-year, variations. For example, sodium concentrations increased from 0.55 to 0.72% with the age of the dugong. Strontium concentrations (mean 0.17%) were closely correlated (r = 0.86) with those of barium (mean 4.5 mg kg⁻¹). Zinc concentrations increased from ∼70 to 170 mg kg⁻¹ with dugong age, but also showed shorter-term fluctuations of ∼30 mg kg⁻¹ that were correlated (r = 0.41) with mean annual Fremantle sea level (a measure of the Southern Oscillation Index and strength of the Leeuwin Current). The concentrations of the elements and correlations with year and between pairs of elements are discussed. Received: 10 January 1997 / Accepted: 21 April 1997     

Spatial variability of nitrous oxide emissions and their soil-related determining factors in an agricultural field

To evaluate spatial variability of nitrous oxide (N2O) emissions and to elucidate their determining factors on a field-scale basis, N2O fluxes and various soil properties were evaluated in a 100- x 100-m onion (Allium cepa L.) field. Nitrous oxide fluxes were determined by a closed chamber method from the one-hundred 10- x 10-m plots. Physical (e.g., bulk density and water content), chemical (e.g., total N and pH), and biological (e.g., microbial biomass C and N) properties were determined from surface soil samples (0-0.1 m) of each plot. Geostatistical analysis was performed to examine spatial variability of both N2O fluxes and soil properties. Multivariate analysis was also conducted to elucidate relationships between soil properties and observed fluxes. Nitrous oxide fluxes were highly variable (average 331 microg N m(-2) h(-1), CV 217%) and were log-normally distributed. Log-transformed N2O fluxes had moderate spatial dependence with a range of >75 m. High N2O fluxes were observed at sites with relatively low elevation. Multivariate analysis indicated that an organic matter factor and a pH factor of the principal component analysis were the main soil-related determining factors of log-transformed N2O fluxes. By combining multivariate analysis with geostatistics, a map of predicted N2O fluxes closely matched the spatial pattern of measured fluxes. The regression equation based on the soil properties explained 56% of the spatially structured variation of the log-transformed N2O fluxes. Site-specific management to regulate organic matter content and water status of a soil could be a promising means of reducing N2O emissions from agricultural fields.     

Juvenile hormone agonists affect the occurrence of male Daphnia

The water flea Daphnia magna reproduces primarily by cyclic parthenogenesis. Environmental stimuli that signal a change to adverse conditions induce the organisms to switch from parthenogenesis to gamogenetic reproduction. During the gamogenetic period, they produce male daphnids and dormant resting eggs, which can survive prolonged periods of environmental adversity. However, little is known about the mechanisms associated with the switch from parthenogenesis to gamogenetic reproduction. We investigated the effects of several juvenoids on sex determination in Daphnia. Females less than 24 h old were exposed to various concentrations of the test substance and were observed for 21 days. It was found that they can trigger the appearance of male daphnids: the percentage of males in the population increases to a level greater than what occurs under ordinary environmental conditions. We found that methylfarnesoate, juvenile hormone III, methoprene, and the phenoxyphenoxy derivatives pyriproxyfen and fenoxycarb (both insecticides) reduced the production of offspring and produced sex ratios dominated by male daphnids. Pyriproxyfen and fenoxycarb showed striking effects at low concentrations. Exposure to either of these chemicals at a concentration of 330 ngl(-1) caused adult females to produce almost all male neonates. Methylfarnesoate, juvenile hormone III, and methoprene showed an effect in inducing male production at higher concentrations (3.7 x 10(3), 3.3 x 10(5), and 1.3 x 10(5) ngl(-1), respectively). Our findings suggest that juvenile hormone agonists, including some insecticides, affect the chemical signaling responsible for inducing the production of male offspring.     

Sensitive monitoring of iodine species in sea water using capillary electrophoresis: vertical profiles of dissolved iodine in the Pacific Ocean

Using a novel high-sensitivity capillary electrophoretic method, vertical distributions of iodate, iodide, total inorganic iodine, dissolved organic iodine and total iodine in the North Pacific Ocean (0-5500 m) were determined without any sample pre-treatment other than UV irradiation before total iodine analysis. An extensive set of data demonstrated that the iodine behaviour in the ocean water collected during a cruise in the North Pacific Ocean in February-March 2003 was not conservative but correlated with variations in concentrations of dissolved oxygen and nutrient elements such as silicon, nitrogen and phosphorus. This suggests that the vertical distribution of iodine is associated with biological activities. The dissolved organic iodine was found in the euphotic zone in accord with observations elsewhere in the oceans. The vertical profile of dissolved organic iodine also appears to be related to biogeochemical activity. The concentrations of all measured iodine species vary noticeably above 1000 m but only minor latitudinal changes occur below 1000 m and slight vertical alterations can be observed below 2400 m. These findings are thought to reflect the stratification of nutrients and iodine species with different biological activities in the water column.     

Temporal moments analysis of preferential solute transport in soils

Temporal moments analysis of solute breakthrough curves is used to investigate the preferential leaching of chloride, nitrate and phosphate through an Australian soil. Recent studies have shown that current models and methods do not adequately describe the leaching of nutrients through soil, often underestimating the risk of groundwater contamination by surface-applied chemicals, and overestimating the concentration of resident solutes. This inaccuracy results primarily from ignoring soil structure and non-equilibrium between soil constituents, water and solutes. Therefore simple models are required to accurately characterise solute transport in natural and agricultural soils under non-equilibrium conditions. A multiple sample percolation system, consisting of 25 individual collection wells was constructed to study the effects of localised soil heterogeneities on the transport of nutrients (NO₃ ^–, Cl^–, PO₄ ^{3 –}) in the vadose zone of an agricultural soil predominantly dominated by clay. Using data collected from the multiple sample percolation experiments, this paper compares and contrasts the performance of temporal moments analysis with two mathematical models for predicting solute transport, the advective-dispersion model with a reaction term (ADR) and a two-region preferential flow model (TRM) suitable for modelling preferential transport. The values for solute transport parameters predicted by temporal moments analysis were in excellent agreement with experimental data and results from ADR and TRM. It is concluded that temporal moments analysis when applied with other physical models such as the ADR and TRM, provide an excellent means of obtaining values for important solute transport parameters and gaining insight of preferential flow. These results have significant ramifications for modelling solute transport and predicting nutrient loadings.     

A GIS-based zoning of illegal dumping potential for efficient surveillance

To assist in the efficient surveillance against illegal dumping, this study examined and evaluated two methods to illustrate the illegal dumping potential of sites using GIS (Geographic Information System) data. One approach focused on the occurrence of illegal dumping sites; the other on the size of the illegal dumping. Both approaches to zoning were implemented for the Kanto region of Japan, utilizing seven or eight major geographical attributes most closely related to illegal dumping. The zoning results revealed the areas requiring patrols against illegal dumping. Evaluation of the zoning results using the ROC (Receiver Operating Characteristic) curve showed the number of illegal dumping sites detectable under certain surveillance conditions and that the size-based zoning was superior, but this superiority was insignificant for revealing sites with higher potential for large illegal dumping, for which it would be sufficient to use the occurrence-based zoning. The evaluation also showed the contribution of each geographical attribute. Finally, application of the ROC curve to the surveillance planning process was examined, which enables the total social cost of pollution by illegal dumping, rehabilitation of dumping sites, and illegal dumping surveillance to be minimized.