Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

Bioavailability to grains of rice of aged and fresh DDD and DDE in soils

DDT had been widely used around the world before 1980s and is still under production and use for non-agricultural purposes in China. Because of their special physicochemical properties, p,p'-DDT and its main metabolites, p,p'-DDD and p,p'-DDE, accumulated and persisted in the environment, presenting potential menace on biota. A green-house study was conducted to determine the bioavailability of p,p'-DDD and p,p'-DDE to grains of rice and the influences of traditional Chinese farming practices on their bioaccumulation. Paddy rice and dry rice were grown in submerged paddy soils and non-submerged upland soils, respectively. Two types of soil, Hydragric Anthrosols (An) and Hydragric Acrisols (Ac), were employed. Bioaccumulation factors (BAFs) of DDE ranged from 0.67 for rice grown in non-submerged An to 0.84 in submerged An in the control group, whilst BAFs were all below 0.04 in experimental groups. BAFs of DDD varied from 1.39 for submerged An to 2.26 for submerged Ac in original soils. In contrast, BAFs were between 0.05 for non-submerged Ac and 0.08 for submerged An in DDD-contaminated soils. Flooding seemed to have two contradictory effects on the DDE/DDD accumulation by rice: on one hand, it made the pollutants more mobile and bioavailable; while on the other hand, it enhanced the degradation and binding of POPs. Adding rice straw to the soils protected DDE from being taken up yet promoted DDD accumulation by rice. Furthermore, the distinct inorganic component of the soils might also play an important role in the environmental activities of POPs.     

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.     

Remobilization of polycyclic aromatic hydrocarbons during the resuspension of Yangtze River sediments using a particle entrainment simulator

Remobilization of 16 polycyclic aromatic hydrocarbons (PAHs) during sediment resuspension was investigated using a particle entrainment simulator at shear stress from 0.2 to 0.5Nm(-2), typical of the energy levels present in many tidally driven aquatic environments. The results suggested that desorption from the entrained particles was the primary source of dissolved PAHs. summation operatorPAHs concentrations in particles on volume normalization increased about four times. However, on mass weight basis, summation operatorPAHs concentrations decreased from 6039.74+/-138.28microgkg(-1) to 1665.39+/-112.26microgkg(-1). The same trend was observed for individual PAHs. Dissolved concentrations of PAHs demonstrated significant differences depending on molecular weight and applied shear. The distribution of PAHs between particle and water phase suggested that for three-ring PAHs, the amounts of PAHs in particles were higher than the predicted values during our experiments. This might be due to presence of another active sorbent.     

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.     

Source analysis of particulate-phase polycyclic aromatic hydrocarbons in an urban atmosphere of a northern city in China

Particle-associated polycyclic aromatic hydrocarbon (PAH) concentrations were investigated at six sampling sites in the heating (February to March 2001) and nonheating (August to September 2001) periods in an industrial city in Northern China. Thirteen PAHs were measured. The total average concentrations (nanograms per meter cubed) of PAHs ranged between 78.93 and 214.63 during the heating period and from 31.48 to 102.26 in the nonheating period. Benzo(a)pyrene occurred at the highest level at a site near an industrial area but occurred at low concentrations far from the city center and industrial areas. In addition, ambient PAH profiles were studied. The five and six-ring species occurred in high fractions at the sampling site. By diagnostic ratio analysis, the major source at each sampling site in the city was coal combustion in the heating period; in the nonheating period, the major sources were relatively complex. Finally, the similarities among the six regions were assessed by principal component analysis, cluster analysis, and coefficient of divergence. These multivariate statistical analyses produced similar results, which agreed with the results from the diagnostic ratio analysis.     

狭长地下受限空间火灾分区形成的试验研究

通过狭长地下受限空间的火灾模拟试验,研究O#柴油在不同空间尺度形成的火灾分区现象.分析柴油燃烧时狭长地下受限空间火灾分区现象形成的判断依据、条件、时间,惰化区氧气耗量与空间容积的关系,惰化区氧气体积分数、烟气温度随时间的变化.结果表明.燃料量、空间尺度和燃烧表面积是影响狭长地下受限空间火灾分区形成的主要因素;分区现象形成的判断依据为惰化区氧气体积分数≤16%;分区现象形成的条件为火焰区容积热强度≥720 kW·m-3.这对地下受限空间火灾的防治和其性能化设计具有参考价值.