Seasonal variation of polycyclic aromatic hydrocarbons in soil and air of Dalian areas, China: an assessment of soil-air exchange

The seasonal variations of concentrations of PAHs in the soil and the air were measured in urban and rural region of Dalian, China in 2007. In soil, mean concentrations of all PAHs in summer were larger than those in winter, whereas the concentrations of heavier weight PAHs in winter were larger than those in summer. Winter/summer concentration ratios for individual PAHs (R(W/S)) increased with the increase of molecular weight of PAHs in soil, indicating that PAHs with high molecular weight were more easily deposited to soil in winter than summer. In air, mean concentrations of all PAHs in winter were larger than those in summer. In comparison with the R(W/S) in soil, all the values of R(W/S) in air were larger than one indicating that the entire individual PAH concentrations in winter were larger than those in summer. The average concentration composition for each PAH compound in soil and air samples was determined and the seasonal change of PAH profile was very small. It was suggested that PAHs in soils and air had the same or similar sources both in winter and summer. The approach to the soil-air equilibrium was assessed by calculating fugacity quotients between soil and air using the soil and air concentrations. The calculated soil-air fugacity quotients indicated that soil acted as a secondary source to the atmosphere for all lighter weight PAHs (two-three rings) and it will continue to be a sink for heavier weight PAHs (five-six rings) in the Dalian environment, both in winter and summer. Medium weight PAHs (four-five rings) were close to the soil-air equilibrium and the tendency shifted between soil and air when season or function region changed. The fugacity quotients of PAHs in summer (mean temperature 298 K) were larger than those in winter (mean temperature 273 K), indicating a higher tendency in summer than winter for PAHs to move from soil to air. The variation of ambient conditions such as temperature, rainfall, etc. can influence the movement of PAHs between soil and air. Most of the fugacity quotients of PAHs for the urban sites were larger than that for the rural site both in winter and summer. This phenomenon may be related with that the temperatures in urban sites were higher than those in the rural site because of the urban heat island effect.     

Behaviour of selected endocrine-disrupting chemicals in three sewage treatment plants of Beijing, China

Occurrence and fate of eight kinds of selected endocrine-disrupting compounds (EDCs) in three sewage treatment plants (STPs) of Beijing, China was investigated. These EDCs, composed of 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), in every step of STPs, were simultaneously analysed by gas chromatography/mass spectrometry after derivatisation. All the EDCs were detected in the influents of three STPs, and BPA was the most abundant compound. The concentrations of EDCs ranged from 36.6 ng/l of 17α-E2 (STP C) to 1342.3 ng/l of BPA (STP B) in the influent sewages and from below limits of detection of E2 and E3 (STP C) to 142.5 ng/l of E1 (STP B) in the effluent sewages. The STPs could not remove alkylphenols effectively from the aqueous phase with less than 40% reduction. BPA decreased over 90%, and steroid estrogens achieved considerable reductions from 64.8% of E2 to 94.9% of E3. Generally, biological treatment was more effective in removing alkylphenols, BPA and natural estrogens from the aqueous phase than primary treatment. However, the synthetic estrogen, EE2, was mostly removed by the primary treatment with about 63.5% reduction. It is the first time that the concentration of 17α-E2 in the sewage of China was reported in this paper. The compound might have a bearing with the waste effluents of dairy farms around urban area of Beijing.     

Multi-scale spatial structure of heavy metals in agricultural soils in Beijing

To effectively investigate the spatial variability of heavy metals in soil, produce a higher quality spatial distribution map, and identify the potential pollution sources of heavy metals, geostatistics was employed to evaluate the effect of scale on spatial variability of heavy metals in Beijing agricultural soils. The results revealed that spatial variability of Cr, Ni, Zn, and Hg was dependent on scale. Validation of the optimality of theoretical semivariance and comparative analysis of the estimation accuracy demonstrated that the multi-scale nested model can reveal the spatial structure of heavy metals effectively and improve the estimation accuracy better than the single-scale method, thereby enabling production a higher quality spatial interpolation map. Thus, the multi-scale kriging nested model is a useful tool for revealing spatial variability of heavy metals in soils, while the spatial distribution maps allow the identification of hot spots with high concentrations of heavy metals.     

Investigations on boron levels in drinking water sources in China

To evaluate boron contamination of public drinking water in China, both dissolved and total boron contents in 98 public drinking water sources from 49 cities, 42 brands of bottled water samples from supermarkets in several cities, and 58 water samples from boron industrial area were measured by inductively coupled plasma-mass spectrometry (ICP-MS). Our experimental results showed that boron existed in public drinking water sources mainly in dissolved status with total concentrations ranging from 0.003 to 0.337 mg/L (mean = 0.046 mg/L). The mean boron concentrations in mineral and pure bottled water were 0.052 and 0.028 mg/L, respectively. The results obtained in this work showed that there was no health risk on view of boron in public drinking water sources and bottled water. In boron industrial area, boron concentrations in surface water and ground water were 1.28 mg/L (range = 0.007–3.8 mg/L) and 18.3 mg/L (range = 0.015–140 mg/L), respectively, which indicated that boron industry caused boron pollution in local water system.     

Investigation of heavy metals in sediments and Manila clams Ruditapes philippinarum from Jiaozhou Bay, China

Manila clams (Ruditapes philippinarum) and sediments were collected bimonthly during 2007 at five locations in Jiaozhou Bay near Qingdao, China, to determine heavy metal concentrations and to assess the validation of R. philippinarum as a metal biomonitor. Concentrations of heavy metals in clam soft tissues ranged between 0.75 and 3.31, 0.89 and 15.20, 5.70 and 26.03, 52.12 and 110.33, 10.30 and 72.34, 9.64 and 28.60, and 3.15 and 52.75 μg g^???1 dry weight for Cd, Pb, Cu, Zn, Mn, Cr, and Ni, respectively. Most of the highest values occurred at the northeast bay and the lowest values occurred at the western part. Regarding seasonal variation, relatively high tissue metal concentrations were observed during October or December. A similar pattern was also found in habitat sediments. There was a strong correlation between the concentrations of Cd, Pb, Zn, Mn, Cr, and Ni in soft tissues and surrounding sediments. It is indicated that R. philippinarum could be used as a biomonitor for heavy metal contamination in Jiaozhou Bay.     

Catalytic activity of Ru/Al2O3 for ozonation of dimethyl phthalate in aqueous solution

With dimethyl phthalate as the model pollutant and Ru/Al(2)O(3) as catalyst, this paper systemically investigates the removal of total organic carbon (TOC) of system. Our results have confirmed that Ru/Al(2)O(3) can significantly increase the effect of ozonation. TOC removal in 120 min can reach 72% while only 24% with ozone alone. The optimal catalyst preparing condition was 0.1 wt% Ru content, 600 degrees C calcination temperature, 0.5-1.0mm particle diameter, which is characterized by a high surface area and a large population of surface active sites. The contrasting experiments of ozone alone, catalyst adsorption after ozonation, and catalytic ozonation confirmed that catalytic reaction was the most important process to TOC removal in system with Ru/Al(2)O(3) as catalyst.     

Decolorization of cationic red X-GRL by wet air oxidation: performance optimization and degradation mechanism

The decolorization of a strong colored azo dye solution of cationic red X-GRL was investigated by wet air oxidation under relatively mild conditions (60-180 degrees C, PO2 = 0-1.2 MPa). Mono-factor experiments were carried out to investigate the effect of the operation factors and the relatively important parameters were selected for optimization using response surface methodology to explore the interactions of these relatively important parameters. Model regeneration analysis and the check experiments showed that the data of the general linear model agreed with the experiment results well. With multistage Monte-Carlo optimization, the best region of these variables could be predicted to dye color removal. At typical operational conditions, the intermediates of dye degradation were detected and confirmed by GC/MS system. Considering the intermediates and the structure analysis with the help of Gaussian 03W (version 6.0) and the theory of dye color, a possible degradation mechanism for the wet air oxidation of cationic red X-GRL was discussed and the probable degradation pathway was deduced.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Heavy metals in bark of <Emphasis Type="Italic">Pinus massoniana</Emphasis> (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang,China

Goal, Scope and Background Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Methods Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO₃. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0–10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Results and Discussion Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Conclusions Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. Recommendations and Perspectives The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.     

炭催化剂吸附剂标准物质的研制

本文介绍了炭催化剂吸附剂标准物质的研制过程。对标准物质的制备技术、均匀性检验、稳定性考察及定值和不确定度进行了逐项分析。采用活性炭浸渍、煅烧技术制得炭催化剂吸附剂标准物质。试验结果表明,该标准物质定值结果准确,均匀性、稳定性良好。铜含量的标准值为11．06％,扩展不确定度为0．13％。