Trends in hazardous trace metal concentrations in aerosols collected in Beijing, China from 2001 to 2006

Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.     

Using turbidity and acoustic backscatter intensity as surrogate measures of suspended sediment concentration in a small subtropical estuary

The suspended sediment concentration is a key element in stream monitoring, although the turbidity and acoustic Doppler backscattering may be suitable surrogate measures. Herein a series of new experiments were conducted in laboratory under controlled conditions using water and mud samples collected in a small subtropical estuary of Eastern Australia. The relationship between suspended sediment concentration and turbidity exhibited a linear relationship, while the relationships between suspended sediment concentration and acoustic backscatter intensity showed a monotonic increase. The calibration curves were affected by both sediment material characteristics and water quality properties, implying that the calibration of an acoustic Doppler system must be performed with the waters and soil materials of the natural system. The results were applied to some field studies in the estuary during which the acoustic Doppler velocimeter was sampled continuously at high frequency. The data yielded the instantaneous suspended sediment flux per unit area in the estuarine zone. They showed some significant fluctuations in instantaneous suspended mass flux, with a net upstream-suspended mass flux during flood tide and net downstream sediment flux during ebb tide. For each tidal cycle, the integration of the suspended sediment flux per unit area data with respect of time yielded some net upstream sediment flux in average.     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

Background There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied. Methods Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted. Results The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air). Discussion Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal. Conclusion Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. Recommendations and Perspective . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.     

Spatio-temporal population dynamics of the sand snail Umbonium costatum: importance of ontogenetic migration and annual recruitment variability

The spatio-temporal population dynamics of the subtidal snail Umbonium costatum (Kiener) in Hakodate Bay, northern Japan, are described over a 9-yr period (1982 to 1988, 1992). Annual variations in recruitment success not only caused the highly variable age structure of the population, but also affected its distribution pattern. In heavy recruitment years (1982, 1984 and 1988), location of the densest population differed from the other years, and the areas with 0 yr old individuals were larger. Every year, the distribution of 0 yr olds was mostly restricted to inshore (within 320 m from shore), while the distribution of adults (>0 yr) was mostly restricted to offshore (>320 m from shore). Such patterns may be generated by ontogenetic migration of cohorts to offshore areas. Ontogenetic migration also could have buffered the large annual variation in spat distribution and maintained the small variation in the distribution of adults. (Prince et al. 1988). Density-related migration has also been reported in Acmaea digitalis (Frank 1965), Patella cochlear (Branch 1974) and Patelloida alticostata (Black 1977).Dense populations of the gastropod Umbonium costatum are found in some clean subtidal sandy-bottoms in Japan, e.g. inner part of Hakodate Bay. In the bay, the age structure of U. costatum revealed predominant year-classes. The 0 yr olds were restricted to the shallowest zone (<4 m depth) and most adult (<0 yr) cohorts were restricted to 6 to 7 m depths (Noda 1991a).This paper describes the temporal variability of population structure and distributional patterns of Umbonium costatum, and examines the distribution-regulating processes.     

Growth and reproduction of the generalist opisthobranch Haloa japonica: effect of algal seasonality on growth rate

The life history of Haloa japonica (Pilsbry), especially the seasonality of growth and reproduction, was investigated from 1992 to 1995 on a flat rocky shore exposed at low tide at Kattoshi, Hakodate Bay, Japan. To estimate the effect of environmental seasonality on growth rate, we conducted two sets of field cage experiments in which algal food was controlled. H. japonica was shown to have an annual life cycle. Spawning occurred from late April to mid-July. Recruitment occurred in June. Simultaneously, large adults disappeared from the habitat. A rapid increase in wet weight of H. japonica was observed in early spring, and coincided with the bloom of the membranous green alga, Monostroma angicava. Under field cage experiments, individuals feeding on both M. angicava and Polysiphonia japonica grew faster than those feeding on only P. japonica. Growth rates of H. japonica feeding on only P. japonica, however, did not vary from February to April. These results suggest that seasonal variation in the algal community limits the growth of H. japonica in early spring at Kattoshi. This factor is relatively more important as a limiting factor on the growth of H. japonica than the physical environment in this season.     

Concentration and trend of 9,10-phenanthrenequinone in airborne particulates collected in Nagasaki city, Japan

9,10-Phenanthrenequinone (PQ), one of the components of atmospheric pollutants, has potent harmful effects on human health. PQ in airborne particulates collected in Nagasaki city was determined by HPLC with fluorescence derivatization. PQ extracted from airborne particulates using methanol was derivatized with benzaldehyde in the presence of ammonium acetate to give a fluorescent compound. The average concentration (mean+/-SD, n=52) of PQ found in airborne particulates collected from July 1997 to June 1998 was 0.287+/-0.128 ng m-3. Concentrations of PQ in winter were higher than those in summer. In a weekly variation study, PQ concentrations were higher during weekdays and lower at weekend. The levels of PQ were obviously correlated with those of phenanthrene (PH) that is considered as a parent compound of PQ. This observation suggested that PQ was emitted into the atmosphere from the same source as PH, or PQ was converted from PH in the atmosphere.     

Formation of dioxin analogs by open-air incineration of waste wood and by fire of buildings and houses concerning Hanshin Great Earthquake in Japan

Ash samples were collected from site of open-air incineration and fire concerning Hanshin Great Earthquake which occurred in western Japan in the early morning of 17 January 1995. The average concentrations of total sum of PCDDs, PCDFs and Co-PCBs in ash collected from wood scrap of broken building fire site, house fire site, shoe-making factory fire site and electric appliances store fire site were 541, 442, 859 and 22,800 pgTEQ/g, respectively. Particularly, PCDFs among dioxin analogs generated remarkably at sites with a high TEQ. In addition, 79,000 t of ash was totally produced at five open-air incineration sites, and consequently the formation amount of PCDDs, PCDFs and Co-PCBs was estimated to be 70.7 gTEQ on the basis of these analytical data.     

Peak wind speed modulation by large-scale motions in neutrally stratified atmospheric surface layer

Environmental Fluid Mechanics - This study applies the models describing the effect of a neutrally stratified high-Reynolds-number boundary layer on peak wind estimation. A neutrally stratified...