Pool of Dust Particles over the Asian Continent: Balloon-borne Optical Particle Counter and Ground-based Lidar Measurements at Dunhuang, China

Measurements of aerosols were made in 2001 and 2002 at Dunhuang (40 degrees 00'N, 94 degrees 30'E), China to understand the nature of atmospheric particles over the desert areas in the Asian continent. Balloon-borne measurements with an optical particle counter suggested that particle size and concentration had noticeable peaks in super micron size range not only in the boundary mixing layer but also in the free troposphere. Super-micron particle concentration largely decreased in the mid tropopause (from 5 to 10 km; above sea level, a.s.l.). Lidar measurements made during August 2002 at Dunhuang suggested the possibility that mixing of dust particles occurred from near the ground to about 6 km even under calm weather conditions, and a large depolarization ratio of particulate matter was found in the aerosol layer. The top of the aerosol layer was found at heights of nearly 6 km (a.s.l.). It is strongly suggested that nonspherical dust particles (Kosa particles) frequently diffused in the free atmosphere over the Taklamakan desert through small-scale turbulences and are possible sources of dust particles of weak Kosa events that have been identified in the free troposphere not only in spring but also in summer over Japanese archipelago. Electron microscopic experiments of the particles collected in the free troposphere confirmed that coarse and nonspherical particles observed by the mineral particle were major components of coarse mode (diameter larger than 1 microm) below about 5 km over Dunhuang, China.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Extraction and cleanup methods of dioxins in house dust from two cities in Japan using accelerated solvent extraction and a disposable multi-layer silica-gel cartridge

A simple and rapid method for the extraction and cleanup of dioxins from house dust was developed using an accelerated solvent extraction (ASE) method and a multi-layer silica-gel cartridge. It was found that the WHO-TEQ levels of dioxins extracted from the house dust obtained by both a conventional soxhlet extraction and the ASE were almost equal, when the data obtained by both methods were compared. As for the cleanup method, a multi-layer silica-gel cartridge yielded higher dioxin recoveries than the alkaline digestion method. The average values of the dioxins in house dust from Kumagaya city and Sendai city in Japan (Sendai city is bigger than Kumagaya city with respect to the population and industry), were 15.6 pg TEQ/g (8.6-26.0 pg TEQ/g, n=5, Kumagaya city) and 16.0 pg TEQ/g (5.9-30.5 pg TEQ/g, n=5, Sendai city), respectively.     

Heterogeneous Sulfate Formation on Dust Surface and Its Dependence on Mineralogy: Balloon-Borne Observations from Balloon-Borne Measurements in The Surface Atmosphere of Beijing, China

This study focuses on providing a direct insight into the process by which sulfate is formed on mineral dust surface in the actual atmosphere. Six sets of aerosol measurements were conducted in the outskirts of Beijing, China, in 2002–2003 using a tethered balloon. The mineralogy of individual dust particles, as well as its influence on the S (sulfur) loadings was investigated by SEM-EDX analysis of the directly collected particles. The mixed layer in the urban atmosphere was found to be quite low (500–600m), often appearing as a particle dense stagnant layer above the surface. It is suggested that mineral dust is a common and important fraction of the coarse particles in Beijing (35–68%), and that it is relatively enriched with Calcite (>28%). An exceptional amount of S was detected in the mineral particles, which can be explained neither by their original composition, nor by coagulation processes between the submicron sulfates and the dust. Heterogeneous uptake of gaseous SO₂, and its subsequent oxidation on dust was suggested as the main pathway that has actually taken place in the ambient environment. The mineral class found with the largest number of particles containing S was Calcite, followed by Dolomite, Clay, Amphibole etc., Feldspar, and Quartz. Among them, Calcite and Dolomite showed distinctly higher efficiency in collecting sulfate than the other types. A positive correlation was found with the number of S containing particles and the relative humidity. Calcite in particular, since almost all of its particles was found to contain S above 60% r.h. On the other hand, the active uptake of SO₂ by the carbonates was not suggested in the free troposphere downwind, and all the mineral classes exhibited similar S content. Relative humidity in the free troposphere was suggested as the key factor controlling the SO₂ uptake among the mineral types. In terms of sulfate loadings, the relationship was not linear, but rather increased exponentially as a function of relative humidity. The humidity-dependent uptake capacity of mineral types altogether showed an intermediate value of 0.07 gSO₄ ²⁻ g⁻¹ mineral at 30% r.h. and 0.40 gSO₄ ²⁻ g⁻¹ mineral at 80%, which is fairly consistent with laboratory experiments.     

Features in Number Concentration-Size Distributions of Aerosols in the Free Atmosphere over the Desert Areas in the Asian Continent: Balloon-Borne Measurements at Dunhuang,China

Vertical changes of aerosol concentration and size in the freetroposphere over the Asian desert areas were firstly observed using a balloon-borne optical particle counter at DunHuang, China (40°00N, 94°30E) (17 August and 17 October 2001, and 11 January 2002). In the free troposphere highly concentrated aerosol layers were frequentlyobserved, suggesting the importance of regional scale particletransportation over the Asian continent. Concentration ofparticles with a diameter larger than 0.15 m was about 5–10particles cm^-3 in the free troposphere.Particle number-size distribution in the free troposphereshows important contribution of super micron particles. Regionalscale transportation, in addition to diffusion of soil particlesfrom the lower atmosphere to the free troposphere through localand small scale air motions, is suggested by backward trajectoryanalysis of air masses containing super micron particles. The importance of horizontal transport of coarse size particles in the free troposphere was strongly suggested.Thickness of the boundary mixing layer, from distributions ofparticle concentration, was about 4 km in summer (17 August 2001)and apparently higher than the height of layers in fall (17 October2001) and in winter (11 January 2002), which suggest an active mixingof particles near the boundary in summer. In winter measurement(11 January 2002), strong inversion was found in the vertical profile of temperature, suggesting cold ground surface and vertically stable atmosphere near the ground.     

Comparison of the Chemical Composition of Mineral Particles Collected in Dunhuang,China and those Collected in the Free Troposphere over Japan: Possible Chemical Modification during Long-Range Transport

The Asian continent is recognized as one of the most important sources of mineral (or soil) particles. These particles have a large potential to effect global changes through the biogeochemical cycle of particulates and through radiative balance (IPCC Third Assessment Report, 2001). Therefore, comparison of particle compositions near the source region and those after long-range transport is important in understanding the long-range particle transport phenomenon. Individual aerosolparticles were collected in Dunhuang (40°09N; 94°41E), China. Particles were collected at the campus of the Meteorological Bureau of Dunhuang City (17 August 2001) and near the Mogao Grots, located approximately 30 km from Dunhuang (18 August 2001, 18 October 2001 and 13 January 2002) using a two-stage low-volume impactor. The morphology of individual aerosol particles and their elemental compositions were examined via a scanning electron microscope (Hitachi, S-3000N) equipped with an energy dispersive X-ray (EDX) analyzer (Horiba, EMAX-500). The particles collected at these locations were comprised primarily of minerals, with the exception of sulphateparticles in the submicron range that were contained in thesample collected on 18 October 2001 (likely, ammonium sulphate). The most abundant elements were found to be Si and Al. Approximately 46–77% of the collected particles were Si-richparticles (composed primarily of quartz and aluminosilicate),and 13–41% of the collected particles were Ca-rich particles,such as calcite (CaCO₃), dolomite (CaMg(CO₃)₂),and gypsum (CaSO₄2H₂O). The fractions of Fe-rich, Mg-rich, Ti-rich, K-rich, and Cl-rich were 3–10, 0–7, 0–3, 0–1, and 0–1%, respectively. Similar types of mineral particles were found in the free troposphere over Japan(Trochkine et al., 2002). A number of differences were found to exist between the particles collected in China and thosecollected in Japan, and these differences can be explained bychemical modification of the particles during transport fromChina to Japan.     

GC/MS analysis of polybrominated diphenyl ethers in fish collected from the Inland Sea of Seto, Japan

Development of an analytical method for polybrominated diphenyl ethers (PBDEs) in fish and their concentration in Japanese marine fish were investigated. Fish homogenate was extracted with diethyl ether/hexane (1 + 3). The extract was cleaned up by automated gel permeation chromatography (GPC) and then by mini-column chromatography, which consisted of three layers of silica gel and sulfuric acid-impregnated silica gel. The PBDE fraction was concentrated and injected into a GC/MS with negative chemical ionization (NCl). Recoveries of the 15 individual PBDEs (BDE-15, 28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, and 209) each at a fortification level of 4 ng/g lipid were in the range of 88-128% and the relative standard deviations (RSD) were 0.43-7.6% (n = 4). Seven species of marine fish (conger eel, flounder, gray mullet, horse mackerel, red sea bream, sea bass, and yellowtail) were collected from the Inland Sea of Seto, and were analyzed with the developed method. Seven PBDEs (BDE-28, 47, 66, 99, 100, 153, and 154) were detected in all the samples. The most abundant PBDE congener was BDE-47 found in all the samples. Relatively high levels of PBDEs were found in the gray mullets and yellowtails.     

Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.     

Feature of Dust Particles in the Spring Free Troposphere over Dunhuang in Northwestern China: Electron Microscopic Experiments on Individual Particles Collected with a Balloon-borne Impactor

Free tropospheric aerosol particles were collected using a balloon-borne particle impactor in August of 2002 and March of 2003 at Dunhuang in northwestern China (40°00′N, 94°30′E), and the morphology and elemental composition of the aerosol particles were analyzed in order to understand the mixing state of coarse dust particles (diameter >1 μm) over the desert areas in the Asian continent in spring. Electron microscopic experiments on the particles revealed that dust particles were major constituents of coarse mode particles in the free troposphere over the Taklamakan Desert in spring and summer. Si-rich or Ca-rich particles are major components of dust particles collected in the free troposphere over dunhuang and the values of [number of Ca-rich particles]/[number of Si-rich particles] differs markedly between spring and summer, being about 0.3 in the spring of 2003 and about 1.0 in the summer of 2002 at heights 3–5 km above sea level. It is likely that the condition of the ground surface and the strength of vertical mixing in source areas of Asian dust are potential factors causing the difference in the chemical types of dust particles. Comparison of the elemental compositions of these particles with those of particles collected over Japan strongly suggests that these particles were chemically modified during their long-range transport in the free troposphere. Analysis of wind systems shows that both the predominating westerly wind in the free troposphere and the surface wind strongly controlled by the geographical structure of the Tarim Basin are important in the long-range transport of KOSA particles originating in the Taklamakan Desert.     

Development of dioxin toxicity evaluation method in human milk by enzyme-linked immunosorbent assay--assay validation for human milk

In this study, the development of a toxicity evaluation method for dioxins in human milk by enzyme-linked immunosorbent assay (ELISA) was reported. A total of 17 human milk samples were tested by ELISA and by gas chromatography/mass spectrometry (GC/MS) to assess whether the ELISA performed on samples obtained from primiparas could be considered as reliable enough for identifying a dioxins contamination in human milk. The concept of toxicity equivalent quantity (TEQ) screening was validated by comparing TEQ values for a set of human milk samples to the ELISA responses predicted for those samples. A fairly good correlation (r=0.920) between immunoassay and GC/MS was achieved for human milk. This ELISA should be useful for biological samples monitoring.