Baseline values for metals in soils on Fildes Peninsula, King George Island, Antarctica: the extent of anthropogenic pollution

Metal contents (Al, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Ti, and Zn) have been measured in 30 surface soils on Fildes Peninsula, King George Island, Antarctica, yielding values (in milligrams kilogram(-1)) of 41.57-80.65 (Zn), 2.76-60.52 (Pb), 0.04-0.34 (Cd), 7.18-25.03 (Ni), 43,255-70,534 (Fe), 449-1,401 (Mn), 17.10-64.90 (Cr), 1,440-25,684 (Mg), 10,941-49,354 (Ca), 51.10-176.50 (Cu), 4,388-12,707 (Ti), 28,038-83,849 (Al), and for Hg (in nanograms gram(-1)) 0.01-0.06. Relative cumulative frequency analysis was used to determine the baseline values for the 13 metals. Compared with adjacent areas in Antarctica, Mg and Ni are significantly lower, but Cu is significantly higher than that of McMurdo Station. Enrichment factor analysis and the geo-accumulation index method were applied in order to determine the extent of anthropogenic contamination, and both show that Pb, Cd, and Hg have been significantly increased by human activities. Principal component analysis was used to identify the sources of metals in these soil samples.     

Risk assessment of heavy metals in road and soil dusts within PM2.5, PM10 and PM100 fractions in Dongying city, Shandong Province, China

15 road and 14 soil dust samples were collected from an oilfield city, Dongying, from 11/2009-4/2010 and analyzed by inductively coupled plasma-mass spectroscopy (ICP-MS) for V, Cr, Mn, Co, Ni, Cu, Zn, As, Cd and Pb within PM(2.5), PM(10) and PM(100) fractions synchronously. Metal concentrations, sources and human health risk were studied. Results showed that both soil and road dust exhibited higher values for Mn and Zn and lower values for Co and Cd for the three fractions. Mass concentration ratios of PM(2.5)/PM(10) and PM(10)/PM(100) for metals in road and soil dust indicate that most of the heavy metals tend to concentrate in fine particles. Geoaccumulation index and enrichment factors analysis showed that Cu, Zn and Cd exhibited moderate or heavy contamination and significant enrichment, indicating the influence of anthropogenic sources. Vanadium, Cr, Mn and Co were mostly not enriched and were mainly influenced by crustal sources. For Ni, As and Pb, they ranged from not enriched to moderately enriched and were influenced by both crustal materials and anthropogenic sources. The conclusions were confirmed by multivariate analysis methods. Principle component analysis revealed that the major sources were vehicle emission, industrial activities, coal combustion, agricultural activities and crustal materials. The risk assessment results indicated that metal ingestion appeared to be the main exposure route followed by dermal contact. The most likely cause for cancer and other health risks are both the fine particles of soil and road dusts.     

Investigation into organic phosphorus species in sediments of Baiyangdian Lake in China measured by fractionation and 31P NMR

Organic phosphorus (OP) species in sediments of the Baiyangdian Lake in China was investigated via fractionation and phosphorus-31 nuclear magnetic resonance ((31)P NMR) spectroscopy. Results of chemical fractionation showed that different OP fractions ranked in the order: humic acid-P?>?HCl-OP?>?fulvic acid-P?≈?NaHCO(3)-OP?>?residual OP. Labile OP and moderately labile OP, which can be degraded for phytoplankton uptake, contributed to 58.7-68.5% of total extracted OP, indicative of the potential P release from sediments in the lake. (31)P NMR spectroscopy results suggested the rank order of P species present in the NaOH-EDTA extractant of the sediments: orthophosphate?>?monoester-P?>?DNA-P?>?pyrophosphate-P. Phytate, polyphosphates, and phosphonates, which appeared in sediments of some deeper lakes, were not detected in the shallow lake. Significant correlations were identified between total P (TP) in water column and sediment TP, monoester-P and DNA-P, positively indicating that sediment P species, especially OP components, should probably contribute to the contents of P in water column and further to the lake eutrophication.     

Characteristics and assessment of phthalate esters in urban dusts in Guangzhou city, China

Phthalate esters (PAEs) were examined in indoor and outdoor dust samples from the subtropical city of Guangzhou, China. The ∑(16)PAEs concentrations ranged from 121 to 3,223 μg g(-1) dust, with the median concentration of 840 μg g(-1) dust. Significantly higher concentrations of PAEs in dust samples were found in offices where electrical and electronic devices, carpet pads, and office furniture were widely used. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in indoor and outdoor dust samples, and accounted for >96.8% and >93.1% of the ∑(16)PAEs concentrations, respectively. The median daily inhalation exposure of ∑(16)PAEs were 3.53 and 0.247 μg kg(-1) body weight day(-1), and at the 95(th) percentile were 7.62 and 0.530 μg kg(-1) body weight day(-1), up on the measured concentrations and estimated dust ingestion rates, respectively, for toddles and adults. The ubiquitous distribution of PAEs as noted in this study suggests the need for detailed assessment of PAEs concentrations using more sites and to further investigate the factors influencing PAEs exposure in China.     

Molecular detection of three gastroenteritis viruses in urban surface waters in Beijing and correlation with levels of fecal indicator bacteria

To assess the presence of three gastroenteritis viruses responsible for human acute gastroenteritis in surface water, a 1-year study was carried out in the city of Beijing, China. A total of 108 urban surface water samples were collected from nine collection sites which were defined with a global positioning system in rivers or lakes from September 2006 to August 2007. The water samples were subjected to virus concentration using an HA electronegative filter, followed by polymerase chain reaction (PCR) for rotavirus (RV) astrovirus (AV), and norovirus (NV). It showed that the number of viruses detected in water samples from different sites was variable, totaling 63 virus strains, with rotavirus (48.1%) verified as the most prevalent detected, followed by astrovirus (AV, 5.6%), and norovirus (NV, 4.6%). RV was also quantified by real-time PCR and the concentration of RV ranged from 0 to 18.27 genome copies·L(-1). And the distributions of RV in surface water were abundant in cold weather (from September to February) while less prevailing in warm weather (from March to August). The high detection rate of RV we encountered in this study provided convincing evidence that RV circulated at a certain frequency in the Beijing population. There was no statistically significant correlation between RV levels and both fecal coliform (R (2)?=?0.02) and Enterococcus faecalis (R (2)?=?0.02) densities. Our study suggests prolonged virus persistence in aquatic environments and emphasizes the enteric virus group as the most reliable for environmental monitoring.     

Chemical compositions and sources of atmospheric PM10 in heating, non-heating and sand periods at a coal-based city in northeastern China

Mass concentrations and chemical components (18 elements, 9 ions, organic carbon [OC] and elemental carbon [EC]) in atmospheric PM(10) were measured at five sites in Fushun during heating, non-heating and sand periods in 2006-2007. PM(10) mass concentrations varied from 62.0 to 226.3 μg m(-3), with 21% of the total samples' mass concentrations exceeding the Chinese national secondary standard value of 150 μg m(-3), mainly concentrated in heating and sand periods. Crustal elements, trace elements, water-soluble ions, OC and EC represented 20-47%, 2-9%, 13-34%, 15-34% and 13-25% of the particulate matter mass concentrations, respectively. OC and crustal elements exhibited the highest mass percentages, at 27-34% and 30-47% during heating and sand period. Local agricultural residuals burning may contribute to EC and ion concentrations, as shown by ion temporal variation and OC and EC correlation analysis. Heavy metals (Cr, Ni, Zn, Cu and Mn) from coal combustion and industrial processes should be paid attention to in heating and sand periods. The anion/cation ratios exhibited their highest values for the background site with the influence of stationary sources on its upper wind direction during the sand period. Secondary organic carbon were 1.6-21.7, 1.5-23.0, 0.4-17.0, 0.2-33.0 and 0.2-21.1 μg m(-3), accounting for 20-77%, 44-88%, 4-77%, 8-69% and 4-73% of OC for the five sampling sites ZQ, DZ, XH, WH and SK, respectively. From the temporal and spatial variation analysis of major species, coal combustion, agricultural residual burning and industrial emission including dust re-suspended from raw material storage piles were important sources for atmospheric PM(10) in Fushun at heating, non-heating and sand periods, respectively. It was confirmed by principal component analysis that coal combustion, vehicle emission, industrial activities, soil dust, cement and construction dust and biomass burning were the main sources for PM(10) in this coal-based city.     

Chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in surface sediment from Taihu Lake, China

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.     

Occurrence and behaviour of nonylphenol and octylphenol in Nanming River, Guiyang City, China

Occurrence, variation and behaviour of nonylphenol (NP) and octylphenol (OP) were studied in surface water and groundwater in Guiyang, Guizhou Province, southwestern China. Discharge of wastewater from Guiyang City was the main source of alkylphenols (APs) entering the aquatic environment. The concentrations of NP and OP in river water ranged from 40 to 1582 ng L(-1) and from below the lowest limit of detection (LOD) to 67 ng L(-1), respectively. NP and OP were also detected in groundwater. Both NP and OP exhibited spatial and temporal variations in river water and groundwater. It was found that concentrations of NP and OP in river water was low upstream and dramatically increased downstream, and higher concentration of NP was found in winter compared to that in summer. Proportions of NP and OP were trapped by suspended particulate matter (SPM), which accounted for 7.6-50.0% and 3.4-25.6% of their total concentration in the river water system, respectively. Seasonal changes in water flow were responsible for the temporal variations of APs. To determine the behaviour of APs along the river, a mass balance equation based on chloride was used. The results showed that a mixing process was the predominant factor to determine upstream APs concentrations; while the discharge of wastewater controlled the concentrations of APs downstream. Considering the adverse effect of APs on organisms, combined effect modeling was used to assess the toxicity to fish. It was found that the predicted mixture effect for APs in river water on fish vitellogenin induction was low upstream and medium downstream, respectively.     

Forensic fingerprinting and source identification of the 2009 Sarnia (Ontario) oil spill

This paper presents a case study in which integrated forensic oil fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of the 2009 Sarnia (Ontario) oil spill incident. The diagnostic fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product-type screening via gas chromatography (GC), analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated PAH (polycyclic aromatic hydrocarbon) homologous series via gas chromatography-mass spectrometry (GC-MS), determination and comparison of a variety of diagnostic ratios of "source-specific marker" compounds, and determination of the weathering degree of the spilled oil, and whether the spilled oil hydrocarbons have been mixed with any other "background" chemicals (biogenic and/or pyrogenic hydrocarbons). The detailed chemical fingerprinting data and results reveal the following: (1) all four samples are mixtures of diesel and lubricating oil with varying percentages of diesel to lube oil. Both samples 1460 and 1462 are majority diesel-range oil mixed with a smaller portion of lube oil. Sample 1461 contains slightly less diesel-range oil. Sample 1463 is majority lubricating-range oil. (2) The diesel in the four diesel/lube oil mixture samples was most likely the same diesel and from the same source. (3) The spill sample 1460 and the suspected-source sample 1462 have nearly identical concentrations and distribution patterns of target analytes including TPHs, n-alkane, PAHs and biomarker compounds; and have nearly identical diagnostic ratios of target compounds as well. Furthermore, a perfect "positive match" correlation line (with all normalized ratio data points falling into the straight correlation line) is clearly demonstrated. It is concluded that the spill oil water sample 1460 (#1, from the water around the vessel enclosed by a boom) matches with the suspected source sample 1462 (#3, from the vessel engine room bilge pump). (4) From the n-alkane and PAH analysis, it appears that the oil in the spill sample 1460 is slightly more weathered in comparison with sample 1462. The minor differences in fingerprints of two samples were most likely caused by weathering effects. (5) Sample 1461 (#2, from the vessel engine room bilge) and sample 1463 (#4, from the vessel bilge waste collection tank) demonstrated significantly different fingerprints and diagnostic ratios of target compounds from that of spill sample 1460. This was caused most likely by percentages of diesel to lube oil in these two samples different from that in spill sample 1460.     

Sorption of phthalate acid esters on black carbon from different sources

Black carbon (BC) is known as a strong sorbent for the sorption of planar hydrophobic organic compounds (HOCs), but there is very little information about the sorption of nonplanar HOCs on BC. In this study, the sorption of di-(2-ethyl-hexyl) phthalate (DEHP), one kind of nonplanar phthalate acid ester (PAE), by environmental BC collected from river sediments and pure BC (char-wood, char-stalk and soot-ash) was investigated. Strong and nonlinear sorption was observed for the sorption of DEHP on both pure BC and environmental BC with the Freundlich exponent ranging from 0.55 to 0.75 except for soot-ash, and the measured K(BC) (BC-water partition coefficient) of DEHP was about one order of magnitude higher than its organic carbon-water partition coefficient. There was a significant difference in sorption capacity among the environmental and pure BC. The presence of di-methyl phthalate (DMP) could significantly decrease the sorption of DEHP on BC, especially for environmental BC. In addition, the contribution of BC to the total sorption of DEHP on original river sediments was more than 50% when the equilibrium concentration of DEHP was less than 10 μg L(-1). This study indicated that ortho-substituted nonplanar PAEs could also be strongly sorbed by BC, and the difference in sorption among the BC samples revealed that it is important to take the source of BC into account when assessing its effects on the fate of HOCs in aquatic environment.