Sulfur speciation and bioaccumulation in camphor tree leaves as atmospheric sulfur indicator analyzed by synchrotron radiation XRF and XANES.

Analyzing and understanding the effects of ambient pollution on plants is getting more and more attention as a topic of environmental biology. A method based on synchrotron radiation X-ray fluorescence and X-ray absorption near edge structure spectroscopy was established to analyze the sulfur concentration and speciation in mature camphor tree leaves (CTLs), which were sampled from 5 local fields in Shanghai, China. Annual SO2 concentration, SO4(2-) concentration in atmospheric particulate, SO4(2-) and sulfur concentration in soil were also analyzed to explore the relationship between ambient sulfur sources and the sulfur nutrient cycling in CTLs. Total sulfur concentration in mature camphor tree leaves was 766-1704 mg/kg. The mainly detected sulfur states and their corresponding compounds were +6 (sulfate, include inorganic sulfate and organic sulfate), +5.2 (sulfonate), +2.2 (suloxides), +0.6 (thiols and thiothers), +0.2 (organic sulfides). Total sulfur concentration was strongly correlated with sulfate proportion with a linear correlation coefficient up to 0.977, which suggested that sulfur accumulated in CTLs as sulfate form. Reduced sulfur compounds (organic sulfides, thiols, thioethers, sulfoxide and sulfonate) assimilation was sufficed to meet the nutrient requirement for growth at a balanced level around 526 mg/kg. The sulfate accumulation mainly caused by atmospheric sulfur pollution such as SO2 and airborne sulfate particulate instead of soil contamination. From urban to suburb place, sulfate in mature CTLs decreased as the atmospheric sulfur pollution reduced, but a dramatic increase presented near the seashore, where the marine sulfate emission and maritime activity pollution were significant. The sulfur concentration and speciation in mature CTLs effectively represented the long-term biological accumulation of atmospheric sulfur pollution in local environment.

Bone-prognostic status after cessation of cadmium exposure for one month in male rats.

This study investigated bone status after decreased cadmium (Cd) exposure in male rats. Sprague-Dawley male rats were randomly divided into three groups. One group was injected subcutaneously with sodium chloride as control. The others were given CdCl2 by subcutaneous injection at doses of 0.5 mg Cd/kg body weight (bw) for 2 months (Cd+2m) and for 3 months (Cd+3m). For the Cd+2m group, the rats were shifted to cessation of Cd injection for 1 month after 2 months' exposure. At month 3, micro-computed tomography (micro-CT) analyses were performed on the proximal tibia and lumbar spine, and urine was collected from all rats. Rats were then killed and blood collected for metabolic-marker measurement and Cd assay. Bone tissues were also collected for bone-mass assay, biomechanical test, and bone-histology analysis. Cd burdens of rats in the Cd+2m and Cd+3m groups were both significantly greater than those in the control group. Cd burdens of rats were lower in the Cd+2m group compared with the Cd+3m group. Bone damage occurred in the Cd+2m and Cd+3m groups compared with the control group (p<0.05), but no significant improvement was found in the Cd+2m group compared with the Cd+3m group. Cd damage to bone could not be reversed over the short term. More attention should be paid to Cd's toxic effects on bone after decreased exposure.

Accumulation and distribution of uranium in rats after implantation with depleted uranium fragments.

PURPOSE: The aim of our study was to clarify the accumulation and distribution of uranium in depleted uranium (DU) implanted rats. MATERIALS AND METHODS: Male Sprague-Dawley rats were surgically implanted in gastrocnemius muscle with DU fragments at 3 dose levels (low, medium and high), and biologically inert tantalum (Ta) fragments were used as controls. At 1 day and 7, 30, 90, 180 and 360 days after implantation, the rats were euthanized and tissue samples including serum and urine were collected to analyze the uranium levels by inductively coupled plasma-mass spectrometry (ICP-MS). RESULTS: At all time points, uranium levels in all the DU implanted groups were higher than that in Ta control group, and uranium concentrations in kidney and bone were significantly greater than that in other tissues. Otherwise, uranium concentrations increased with a close correlation to the implanted DU doses and duration of exposure, with a peak at 90 days post-implantation, after which followed by a decreasing period, but still maintained at a relatively high level even at 360 days post- implantation. The uranium concentrations in bone were 6.92 +/- 0.97 microg U/g, 16.35 +/- 1.67 microg U/g and 21.64 +/- 3.68 microg U/g in the low-, medium- and high-dose group animals, while values in kidney tissues were 10.66 +/- 1.10 microg U/g, 14.06 +/- 1.28 microg U/g and 17.79 +/- 2.87 microg U/g, respectively, at 360 days post-implantation. CONCLUSION: It was concluded that kidney and bone are the primary reservoirs for uranium redistributed from intramuscularly embedded fragments, and the accumulations in kidney, bone and many other tissues suggest the potential for unanticipated physiological consequences of chronic exposure to DU.

Atmospheric lead pollution in fine particulate matter in Shanghai, China.

The Pb-monitoring program was extended for 6 years from 2002 to 2007 at 17 representative urban sites (6 traffic, 5 industrial, and 6 residential sites), and 3 suburban sites to assess the lead pollution in fine particulate matter (PM2.5) after phasing out leaded gasoline in Shanghai. Compared with Pb levels reported in other places, the Pb pollution in Shanghai is still serious after phasing out leaded gasoline, which remains at high concentration range (213-176 ng/m3) in PM2.5 in winter. Significant spatial variation of Pb concentrations and strong seasonal variation of higher Pb concentration in winter than that in summer were detected. The size distribution of Pb in particulate matter has a unimodal mode that peaks at approximately 0.154-1.59 microm particle diameter, indicating that Pb is mainly concentrated in fine fraction. Lead in the fine fraction is enriched by a factor of 10(3)-10(4) relative to Pb abundance in crust. Eight categories of Pb pollution sources were identified in the PM2.5 in the winter of 2007 in Shanghai. The important emission sources among them are vehicle exhaust derived from combustion of unleaded gasoline, metallurgic industry emission, and coal combustion emission.

Characteristics of trace elements and lead isotope ratios in PM(2.5) from four sites in Shanghai.

PM(2.5) samples were collected in Shanghai at four sites with different typical land-uses. The sampling was done concurrently once per month from April 2004 to April 2005, and the ambient mass concentration, the elemental composition and the stable lead isotope ratios in these PM(2.5) samples were determined. The annual average concentrations of PM(2.5) samples at each site were 84+/-30, 65+/-20, 55+/-18, and 41+/-10 microg m(-3), respectively, indicating there were severe air pollution levels in Shanghai. The enrichment factor was calculated for each element and the comparison and discussion of elements with significant anthropogenic contributions between Shanghai and Tokyo suggested that the major source of PM(2.5) in Shanghai was not traffic-derived emissions, but the stationary industrial contribution emitted from coal use. Moreover, the analysis of stable lead isotope ratios revealed only a slight difference within the samples at the four sites which fell well within the scope of coal composition difference, further confirming that the contribution from stationary industrial emissions to atmospheric lead pollution of PM(2.5) was very substantial in Shanghai.

Determination of plutonium isotopes in freshwater lake sediments by sector-field ICP-MS after separation using ion-exchange chromatography.

The determination of Pu isotopes in lake sediments is important for many studies, such as Pu pollution source identification, sediment mixing estimation, erosion evaluation and establishment of deposition chronology in lakes. In this paper, a simple analytical method using sector field inductively coupled plasma mass spectrometry (ICP-MS) combined with two-stage chromatographic separation and purification of Pu was developed based on the optimization and adaptation of the previously published method for marine samples with an emphasis on the study of the elimination of interferences for the analysis of freshwater lake sediments. A strong base anion-exchange resin (AG MP-1M) was used to purify Pu isotopes with concentrated HBr as the final eluent for Pu elution. The chemical yields were ca. 64% and the decontamination factor for U was ca. 10(5). The developed method was validated using a freshwater lake sediment reference material (SRM-4354) and a marine sediment reference material (IAEA-368), and applied to the determination of Pu isotopes in sediment samples of Lake Poyang, East China. For the analysis of certified reference materials, both 239+240Pu activity of 31.6 mBq g(-1) and 240Pu/239Pu atom ratio of 0.033 for IAEA-368 were comparable to the certified value and/or literature values. As for SRM-4354, 239+240Pu activity of 3.90 mBq g(-1) agreed well with the certified value. However, the mean 240Pu/239Pu atom ratio of 0.144 was lower than those reported by other laboratories. This difference suggested that this material may be isotopically inhomogeneous. 240Pu/239Pu atom ratios of Poyang Lake sediment samples ranged from 0.185 to 0.192 with a mean value of 0.187+/-0.004, indicating that plutonium pollution originated from global fallout.

Quantification of extrapulmonary translocation of intratracheal-instilled particles in vivo in rats: effect of lipopolysaccharide.

Particulate air pollution is associated with respiratory and cardiovascular morbidity and mortality. However, important uncertainties remain in the quantification of extrapulmonary translocation of ultrafine particles into blood circulation. Therefore, the widely used radioiodinated technique was applied to radiolabel polystyrene particles with an average diameter of 56.4 and 202 nm, respectively. The extrapulmonary distribution of these particles (3.7 x 10(5) Bq/rat) was quantified at 0.5, 2, 24 and 120 h after intratracheal instillation in rats. Moreover, we have taken into account the possible involvement of pulmonary inflammation in this process. Rats which received a single intratracheal instillation of free 125I or a single intravenous injection of labeled ultrafine particles served as control. The results indicated that the pulmonary deposition of radioactivity was almost unchanged for both sizes. Only small amounts of radioactivity (1.64-2.49%) were recovered in blood shortly after administration of both types of particle, in healthy rats. However, the extent of particle translocation into the blood of the ultrafine size following the pretreatment with lipopolysaccharides was significantly higher (from 1.96 +/- 0.67 to 4.73 +/- 0.31%) compared to larger particles (from 2.19 +/- 0.77 to 2.21 +/- 0.64%). In conclusion, our findings suggest that only a small fraction of intratracheal-instilled ultrafine particles can pass rapidly into systemic circulation, but this translocation is markedly increased following LPS pretreatment. Thus, pulmonary inflammation seems to play a major role in enhancing the extrapulmonary translocation of particles.

Elemental contents in serum of pregnant women with gestational diabetes mellitus.

Diabetes mellitus is characterized by hyperglycemia and is closely related to trace elements. Quite a few pregnant women suffer from impaired glucose tolerance (IGT) or gestational diabetes mellitus (GDM). Investigation of the changes of elemental contents in serum of the pregnant women with IGT and GDM is significant in the etiological research and cure of the diseases. In the present work, the elements Cu, Zn, Ca, Sr, Mg, P, Fe, and Al in the serum of pregnant women were determined. The elemental contents in different experimental groups were compared. Also, the correlation between elemental contents and gestational period was observed. The results showed that compared with normal pregnant women, the Cu contents in serum of pregnant women with GDM increased, but Zn contents had a decreasing trend. In addition, for all pregnant women, the Ca contents in serum had an obvious inverse correlation with gestational period.

[Study on transition metals in airborne particulate matter in Shanghai city's subway].

PM10 and PM2.5 aerosol particle samples were collected at a subway station in Shanghai and their morphology, chemical composition and transition metal species were studied. The mass concentrations of PM10 and PM2.5 inside the subway station were significantly higher than those measured in aboveground ambient air. The PM levels inside subway were much higher than the state control limit. The aerosol composition in the metro station was quite different from that of the aboveground urban particles. Concentrations of Fe, Mn and Cr were higher than the averages of aboveground urban air particles by factors of 8, 2, and 2, respectively, showing a substantial enrichment in subway. Scanning electron microscope (SEM) analysis showed that the subway particles had flat surfaces in combination with parallel scratches and sharp edges and looked like metal sheets or flakes. Furthermore, analysis of the atomic composition of typical subway particles by energy dispersive X-Ray (EDX) spectroscopy showed that oxygen and iron dominated the mass of the particles. The X-ray absorption near-edge structure (XANES) spectroscopy results showed that a fraction (> 26%) of the total iron in the PM10 was in the form of pure Fe, while in the street particles Fe(III) was shown to be a significant fraction of the total iron. The work demonstrated that the underground subway stations in Shanghai were an important microenvironment for exposure to transition metal aerosol for the people taking subway train for commuting every day and those who work in the subway stations, and the metal particle exposure for people in the subway station should not be ignored.

Lead concentration in plasma as a biomarker of exposure and risk, and modification of toxicity by δ-aminolevulinic acid dehydratase gene polymorphism.

UNLABELLED: Blood lead concentration (B-Pb), the main biomarker of lead exposure and risk, is curvi-linearily related to exposure. We assessed plasma lead (P-Pb) as a marker for both lead exposure and toxic effects. We examined claims that δ-aminolevulinic acid dehydratase genotype (ALAD) can modify lead toxicity. In 290 lead-exposed and 91 unexposed Chinese workers, we determined P-Pb, B-Pb, urinary lead (U-Pb), ALAD polymorphism (rs1800435, ALAD1/2; TaqMan assay), and also toxic effects on heme synthesis (blood zinc protoporphyrin and hemoglobin, urinary δ-aminolevulic acid), on the kidneys (urinary albumin, ß2-microglobulin and N-acetyl-ß-d-glucosaminidase) and on the peripheral nervous system (sensory and motor conduction velocities). In exposed workers, median P-Pb was 4.10 (range 0.35-27)µg/L, B-Pb 401 (110-950)µg/L, and U-Pb 188 (22-590)µg/g creatinine. P-Pb had a higher ratio between exposed and unexposed workers (median 39, range 18-110) than B-Pb (19, 15-36; p<0.001) and U-Pb (28, 15-36; p<0.001). All three biomarkers were associated with all toxic effects (P-Pb: rS=-0.10 to 0.79; B-Pb: rS=-0.08 to 0.75; all p<0.05). In the exposed workers, B-Pb and U-Pb were significantly higher (p=0.04) in ALAD2 carriers (7% in the exposed population) than in ALAD1 homozygotes. P-Pb values were similar; ALAD1 homozygotes suffered higher kidney toxicity at the same P-Pb. CONCLUSIONS: (i) P-Pb has advantages over B-Pb as a biomarker of high Pb exposure, but it was not significantly better as an index of risk of toxicity. (ii) The ALAD genotype modifies toxicokinetics and toxicodynamics.

Environmental lead pollution threatens the children living in the Pearl River Delta region, China.

INTRODUCTION AND PURPOSE: The objective of this study is to determine children's blood lead levels and identify sources of lead exposure. Childhood lead exposure constitutes a major pediatric health problem today in China. A blood lead screening survey program for children in the age group of 2-12 years residing in Pearl River Delta region, south of China, was carried out from Dec 2007 to Jan 2008. METHODS: Blood lead levels and lead isotope ratios of a total of 761 participants were assessed by inductively coupled plasma mass spectroscopy. Measurements of urban environmental samples for source identification of children lead exposure were also performed. RESULTS AND CONCLUSIONS: The geometric mean value of the children's blood lead levels was 57.05 µg/L, and 9.6% of them were higher than 100 µg/L. The blood lead levels were still much higher than those in developed countries. Based on the data of environmental lead source inventories, lead isotopic tracing revealed that there is about 6.7% past used gasoline Pb embedded in Shenzhen residential dust and about 15.6% in Guangzhou dust, respectively.

Effects of cadmium on bone microstructure and serum tartrate-resistant acid phosphatase 5b in male rats.

This study investigated the effects of cadmium on bone microstructure and serum tartrate-resistant acid phosphatase 5b (Tracp 5b) in male rats. Sprague-Dawley male rats were divided into three groups that were given CdCl(2) by subcutaneous injection at doses of 0, 0.1 and 0.5 mg/kg body weight (bw) for 12 weeks, respectively. Before killing at the 12th week, microcomputed tomography scanning was performed on the proximal tibia, and urine samples were collected from all of the rats. All rats were then killed, and their blood was collected for biomarkers assay. Bone tissues were dissected for mineral density determinations and histology. The concentration of cadmium in the blood, urine and bone of rats treated with cadmium were significantly higher than in the control group. The bone mineral density, bone mineral concentrations and bone microstructure index of rats treated with cadmium at 0.5 mg/kg bw were clearly lower than in the control rats. Histological investigation also revealed damage to the bone microstructure caused by cadmium. Tracp 5b concentrations in rats treated with cadmium were dose dependently higher than the control. The concentration of cadmium in blood, urine and bone was significantly correlated with Tracp 5b and bone microstructure parameters. Cadmium was shown to induce bone microstructure damage, especially to trabecular bone. The elevated concentrations of serum Tracp 5b suggest that bone resorption mediated via osteoclasts is an important mechanism for the toxic effects of cadmium on bone.

Lead in children's blood is mainly caused by coal-fired ash after phasing out of leaded gasoline in Shanghai.

Lead (Pb) is a highly toxic element to the human body. After phasing out of leaded gasoline we find that the blood lead level of children strongly correlates with the lead concentration in atmospheric particles, and the latter correlates with the coal consumption instead of leaded gasoline. Combined with the (207)Pb/(206)Pb ratio measurements, we find that the coal consumption fly ash is a dominate source of Pb exposure to children in Shanghai, rather than vehicle exhaust, metallurgic dust, paint dust, and drinking water. Those particles are absorbed to children's blood via breathing and digesting their deposition on ground by hand-to-mouth activities. Probably the same situation occurs in other large cities of developing countries where the structure of energy supply is mainly based on coal-combustion.

Total and speciated arsenic levels in rice from China.

Although the need for policy development on arsenic (As) in rice has been recognized and a legally enforceable maximum contaminant level (MCL) for inorganic arsenic (As(i)) in rice has been established in China, evidence reported in this article indicates that the risk of exposure to As for the Chinese population through rice is still underestimated. Polished rice from various production regions of China was analyzed for total As and arsenic species using HPLC-ICPMS. Total As concentration ranged 65.3-274.2 ng g(-1), with an average value of 114.4 ng g(-1). Four arsenic species, including arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA), were detected in most rice samples. The As(i) (As(III) + As(V)) species was predominant, accounting for approximately 72% of the total As in rice, with a mean concentration of 82.0 ng g(-1). In assessing the risk from As in rice, we found that As intake for the Chinese population through rice is higher than from drinking water, with a 37.6% contribution to the maximum tolerable daily intake (MTDI) of As recommended by World Health Organization (WHO), compared with 1.5% from drinking water. Compared to other countries, the risk for the Chinese from exposure to As through rice is more severe due to the large rice consumption in China. Therefore, not only the scientific community but also local authorities should take this risk seriously. Furthermore, more stringent legislation of the MCL for rice should be enacted to protect the Chinese consumer from a high intake of As.

[Comprehensive study of lead pollution in atmospheric aerosol of Shanghai].

The lead contamination, lead species and source assignment were studied by a combination of several analytical techniques such as Proton-induced X-ray emission analysis (PIXE), Proton microprobe (micro-PIXE), Inductively coupled plasma-mass spectrometry (ICP-MS) and extended X-ray absorption fine structure (EXAFS) techniques. The results indicate that the lead concentration in the air of Shanghai gradually decreased over the last years. The atmospheric lead concentration of PM10 in the winter of 2002 was 369 ng x m(-3), which had declined by 28% in 2001, and in the winter of 2003 it decreased further to 237 ng x m(-3). The main lead species in the samples collected in the winter of 2003 were probably PbCl2, PbSO4 and PbO. The source apportionment was calculated in terms of the combination of lead isotope ratios and lead mass balance method, assisted by single particle analysis with micro-PIXE and pattern recognition. The results suggest that the major contributors of atmospheric lead pollution in Shanghai are the coal combustion dust; the metallurgic dust and vehicle exhaust particles, with a contribution around 50%, 35% and 15%, respectively. It probably is the first time to give a city a quantitative estimation of lead pollution contribution from emission sources. The influence from leaded gasoline was still present in the atmosphere by four or five years after the phasing out of leaded gasoline.