Composition and source identification of polycyclic aromatic hydrocarbons in mangrove sediments of Peninsular Malaysia: indication of anthropogenic input

This is a comprehensive study of the composition, origin and sources of specific polycyclic aromatic hydrocarbons (PAHs) in sediments of mangrove estuary in the western part of Peninsular Malaysia. Mangrove sediments were analyzed for 17 PAHs by gas chromatography–mass spectrometry. Total PAH concentrations in the sediments ranged from 20 to 112 ng/g on a dry-weight basis. High molecular weight PAHs were abundant in the sediments. Parent PAH ratios revealed that pyrogenic input has important contribution to the sedimentary PAHs. Ratios of alkylated PAHs indicate that the sedimentary PAHs were influenced by petrogenic PAHs, which implies that petrogenic input has contribution to the sedimentary PAHs but that it is not a major factor in distribution of PAHs within the estuary. Combustion-derived PAHs show a positive and very strong correlation with total PAHs (R ² = 0.926, p < 0.05). Total methylphenanthrenes show very weak correlation with total PAHs (R ² = 0.0928, p < 0.05). The PAH concentrations were found to increase with distance from the upstream of the estuary to the coastal area of the Straits of Malacca. For the assessment of sediment contamination using biological thresholds, none of the individual studied PAH compounds exceeded the values of the effect range low–effect range median guideline and the threshold effects level–probable effects level guideline. This study demonstrates that the sediments of the mangrove ecosystem facing the Straits of Malacca and Sumatra are influenced by anthropogenic PAH inputs as a result of human activities such as biomass burning, vehicle emissions and boating activities.     

Novel aryl polycyclic aromatic hydrocarbons: Phenylphenanthrene and phenylanthracene identification, occurrence and distribution in sedimentary rocks

Numerous reports have recognised the presence of compounds with molecular weight 254 a.m.u. in aromatic fractions. However, their unequivocal identification has not been achieved due to a lack of reference substances. In geological samples, such m/z 254 compounds could potentially be represented by a number of structural isomers of binaphthyl, phenylphenanthrene, phenylanthracene and indenofluorene with each compound type possessing several positional isomers. In this work, all these m/z 254 compounds, with the exception of the tentatively recognised indenofluorenes, have been unequivocally identified in sedimentary rocks for the first time. Comparison of the mass spectra and the gas chromatography (GC) retention times of synthesised standards with the natural compounds in rocks shows that the major components of aromatic fractions are phenylphenanthrene isomers and, to a lesser extent, binaphthyls and 9-phenylanthracene. The elution sequence expressed as standard retention indices of all these m/z 254 isomers were determined by using high resolution capillary GC with three stationary phases: 5%, 35% and 50% (mole fraction) phenyl substituted methylpolysiloxane on HP-5MS, DB-35MS and DB-17MS columns, respectively. A survey of more than 350 sedimentary rock samples of varying origins and maturity (R_r 0.3–1.4%) reveals that relative abundances of the m/z 254 isomers depend on the maturity of the organic matter. The isomers initially appear at the onset of oil generation (R_r > 0.5%) exclusively in diagenetically/catagenetically oxidised samples containing varying proportions of Types II and III kerogen. Interestingly, all five possible positional phenylphenanthrene isomers (including the most sterically hindered isomer 4-phenylphenanthrene) are present from the beginning of the oil generation window. Such a distribution suggests that low-regioselectivity reactions are likely to be involved in the formation. Interaction, during maturation, of phenyl radicals from primary cracking with aromatic moieties of more resistant terrigenic components of kerogen in an oxidising diagenetic realm is postulated to be responsible for the neoformation of phenylated aromatics in geological samples. Up to the final stages of oil generation, the evolution of the phenyl PAH distributions presumably involve 1,2-phenyl shift reactions and cyclisation, if allowed by the molecular geometry. A near thermodynamically-controlled distribution, with only 3- and 2-phenylphenanthrene and minor 2,2′-binaphthyl remaining, is approached when vitrinite reflectance reaches 1.2% (R_r). The three compounds seem to be persistent beyond the oil window as is suggested by their presence in hydrothermal oil formed at T > 300 °C.     

Vertical profile of polycyclic aromatic hydrocarbons in a sediment core from a reservoir in Osaka City

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in a dated sediment core from a reservoir at Osaka City, Southwest Japan. The sediment core consisted of deposits collected over a period of almost 70 years whose PAH content would serve as a historical record of atmospheric environment at Osaka City. Total PAH concentrations varied from 4.2 to 26 mg kg⁻¹ dry wt, and peaked in the 1940s, reflecting the occurrence of a large fire due to air attacks during World War II. The results indicated that warfare had the largest impact on atmospheric environment in Osaka City. Total PAH concentrations decreased in the post-war period except for a small peak. In the 1950s, there was a downward trend from the 1970s to the present. These trends can be ascribed to the growth of industrial activities and the regulation of atmospheric pollutant emissions, respectively.     

The global distribution of polycyclic aromatic hydrocarbons in recent sediments

Polycyclic aromatic hydrocarbons (PAH) and their alkyl homologs are distributed in sediments throughout the world. The qualitative PAH pattern is remarkably constant for most of the locations studied, and the quantitative PAH abundance increases with proximity to urban centers. These findings are consistent with anthropogenic combustion's being the major source of these compounds. Two non-combustion sources of PAH have also been noted: retene coming from abietic acid and perylene probably coming from various extended quinone pigments.     

表层岩溶带土壤中多环芳烃分布特征及来源解析

利用气相色谱-质谱联用仪(GC-MS)对表层岩溶泉域土壤中的16种优控的多环芳烃(Polycyclic Aromatic Hydrocarbons, PAHs)含量进行了分析,并对其组成、污染水平和来源进行了探讨。结果表明,16种优控PAHs在表层岩溶泉域土壤中的检出率为100%,其含量介于439.19~3329.72ng/g之间,平均值为1392.44ng/g,7种致癌性PAHs占总量的26%。PAHs的组成特征受地形的控制,随着海拔升高,低环PAHs所占比例升高,高环PAHs比例降低。同分异构体比值分析表明,研究区土壤中的PAHs主要来自于煤、生物质和石油的燃烧排放。研究区土壤中16种PAHs的TEQcarc值介于18.65~501.13ng/g,平均值为140.57ng/g。7种致癌性PAHs占总TEQcarc的比例达到96.8%。研究区表土中,后沟泉域的污染程度最大,次之是兰花沟泉域和柏树湾泉域,水房泉泉域的污染程度最小,但由于柏树湾泉域松针落叶中BaP、PAHs含量较高,松针落叶中PAHs含量分别高达36.36ng/g和2370.1ng/g,土壤生态风险评价中应考虑松针落叶层的潜在影响。      

Vertical transport of polycyclic aromatic hydrocarbons in different particle-size fractions of sandy soils

Vertical transport of selected polycyclic aromatic hydrocarbons (PAHs) in different particle-size fractions of sandy soils was investigated by simulation experiments in soil columns. Tested soil samples were fractionized into three particle-sizes including sand, coarse silt and fine silt (2,000–50, 50–20 and <20 μm). Rainfall simulations were conducted in artificially PAHs contaminated soil columns with 30 cm length and 5 cm diameter in 40 days. PAHs were extracted from soil samples and determined by high performance liquid chromatography (HPLC). Results showed that the residue level of PAHs in fine silt fraction reached 35.85 mg/kg, which was significantly higher than those in sand and coarse silt fraction (16.28 and 11.80 mg/kg, respectively), probably because PAHs in macroporous fractions were prone to volatilize or degrade compared with that in microporous fractions. Linear relationship between the residue levels of individual PAH (R _PAHs) and the value of partition coefficient (log K _oc) was regressed as R _PAHs = 1.55 × log K _oc − 5.86, R ² = 0.91, n = 9. These results indicated that vertical transport of the mixed PAHs in soils were controlled both by the nature of PAHs (i.e. log K _oc, molecular weight), soil particle size and soil organic contents, which could influence the transport of PAHs.     

Relationship between heavy metals and polycyclic aromatic hydrocarbons in the multi-phases of Nanhu Lake, China

Heavy metals （HMs） and polycyclic aromatic hydrocarbons （PAHs） are two sorts of important pollutants, which were frequently detected in natural aquatic environments at the same time. Surfacial sediments （SSs）, suspended particulates （SPs） and natural surface coatings （NSCs） are recognized as the key solid sinks and sources of heavy metals （HMs） and organic materials （OMs） in natural water systems, playing critical roles in the cycling and transformation of pollutants. The behaviors of HMs in the multi-phases （SSs, SPs and NSCs） have been well investigated, but less reports on those of PAHs, especially on those of HMs and PAHs simultaneously in the multi-phases. Hence, the relationship between HMs （Pb, Cd and Cu） and PAHs （fluorene, phenanthrene, anthracene and pyrene） in the multi-phases of Nanhu Lake in Changchun, China, was studied in this study using methods of acid digestion and extraction, in order to reveal the combined pollution of HMs and PAHs in Nanhu Lake. The information indicated that HMs and PAHs have the similar distribution patterns in the multi-phases of Nanhu Lake, with increasing levels of riMs and PAHs in the SSs, SPs and NSCs. And the enrichment capacities of SPs and NSCs for HMs and PAHs in the water were similar to each other and much greater than that of SSs, implying that SPs and NSCs contributed more to the transference and transformation of HMs and PAHs in the aquatic environments. The relationship between HMs and PAHs has been analyzed by SPSS statistical analysis, and the results showed that the significant correlation of riMs and PAHs was found in the SSs at the confidence level of p = 0.05, but Pb, Cd or Cu had no correlation with any monomer of PAHs in the SPs or NSCs, highlighting the existence of combined pollution of HMs and PAHs in SSs. This was partly due to the relative lability of SPs or NSCs compared to SSs resulting from the water quality of being varied.     

Study of the origin of polycyclic aromatic hydrocarbons in water of Lake Baikal

Doklady Earth Sciences - The concentration of polycyclic aromatic hydrocarbons in the water of Lake Baikal is estimated. The published data on the composition of polycyclic aromatic hydrocarbons in...     

Levels of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in sediment of bitumen deposit impacted area

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls were investigated in sediment of bitumen deposit impacted area of Agbabu, Nigeria, to determine the present level of contamination with these toxic compounds prior to exploitation. Samples were collected during the dry season (March) and the wet season (August) of year 2008. Analysis was carried out with gas chromatography using mass spectrometry detector for polycyclic aromatic hydrocarbons and flame ionization detector for polychlorinated biphenyls. In the dry season sum of concentration of PAHs ranged from zero to 0.12 ± 0.06 ppm, while in the wet season the minimum was 0.18 ± 0.07 ppm and the maximum was 1.04 ± 0.16 ppm. Most of these values were higher than sum of polycyclic aromatic hydrocarbons concentrations of 1–10 μg/kg indicating that they were likely to come from anthropogenic sources. Average concentrations of PAHs such as naphthalene and benzo (a) pyrene obtained in sediment in the wet season in some of the stations were higher than recommended limits. The linear regression analysis between sum of concentrations and percentage organic carbon showed no significant correlation in sediment in the dry season (r² = 0.0025) and in the wet season (r² = 0.1345). The predominance of 4–6 ringed polycyclic aromatic hydrocarbons and the ratios between pairs of individual polycyclic aromatic hydrocarbons showed that they are likely to have come from pyrolytic sources. No polychlorinated biphenyl congener was detected in the samples.     

Variation and correlations of selected heavy metals in sediment and aquatic plants in Tasik Chini,Malaysia

This paper aims to determine the correlation between Cd, Cu and Pb concentration in the sediment and in five aquatic plants sampled during wet, normal and dry seasons. Analyses of the sediment showed that concentrations of exchangeable Cd and Cd after acid reduction were higher during the wet season (October) than on other sampling dates with mean values of 0.18 and 0.29 μg g⁻¹, respectively. The concentration of Cu in the organic oxidation phase was higher in the normal season (January) than on other sampling dates with a mean value of 11.1 μg g⁻¹. The concentrations of exchangeable Pb and that in the residual phase were higher during the wet season than on other sampling dates with mean values of 1.05 and 9.18 μg g⁻¹, respectively. Cd and Pb concentrations in the leaves, stems and roots varied between sampling dates with a reduced concentration during dry season (July) and the highest metal concentrations (Cd and Pb) during wet season. There were positive correlations between Cd and Cu concentrations in the plant tissues (leaves, stems and roots) of most aquatic plants in the acid reduction fraction. Conversely, there was no positive correlation between Pb concentration in the plant tissues of all aquatic plants and the acid reduction fraction of the sediment.     

Risk assessment of polycyclic aromatic hydrocarbons in the West Port semi-enclosed basin (Malaysia)

Sediment samples collected from the West Port, the west coastal waters of Malaysia, were analyzed by standard methods to determine the degree of hydrocarbon contamination and identify the sources of polyaromatic hydrocarbons (PAHs). Concentrations of PAHs in the port sediments ranged from 100.3 to 3,446.9 μg/kg dw. The highest concentrations were observed in stations close to the coastline, locations affected by intensive shipping activities and industrial input. These were dominated by high-molecular-weight PAHs (4–6 rings). Source identification showed that PAHs originated mostly pyrogenically, from the combustion of fossil fuels, grass, wood, and coal or from petroleum combustion. Regarding ecological risk estimation, only station 7 was moderately polluted, the rest of the stations suffered rare or slight adverse biological effects with PAH exposure in surface sediment, suggesting that PAHs are not considered as contaminants of concern in the West Port.     

Application of spatial analysis and multivariate analysis techniques in distribution and source study of polycyclic aromatic hydrocarbons in the topsoil of Beijing,China

Surface soil samples were collected from 161 sites throughout the downtown and suburban area of Beijing, China. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) concentrations. Through Kriging analysis, five heavily contaminated zones were identified in the study area. Sources of PAHs in the soil were apportioned using principal factor analysis and multiple linear regression. Three factors were identified representing coal combustion/vehicle emission, coking emission, and petroleum sources, respectively. The relative contributions of the three sources were 48% for coal/vehicle emission, 28% for coking emission, and 24% for petroleum sources. The contributions of total PAHs from the three sources were 16.4, 4.63 and 3.70 ng g⁻¹, respectively. Spatial analysis indicated that the contribution of coal/vehicle sources was higher in the downtown area than in the suburban area, the petroleum sources had a high contribution in the urban area, and the contribution of coking sources was high in the suburban area. The results indicated that PAH contamination in the surface soil in Beijing was closely related to the spatial characteristics of energy consumption and functional zoning. Improvement of the energy consumption structure and relocation of industries with heavy pollution are effective ways to control PAH contamination in surface soil in the area.     

Sources and distribution of aliphatic and polycyclic aromatic hydrocarbons in Yellow River Delta Nature Reserve, China

Sediment samples collected from the Core Area, Experimental Area and Buffer Area of Yellow River Delta National Nature Reserve (YRDNNR), China, were analyzed by GC-MS in order to determine the degree of hydrocarbon contamination, and identify the sources of aliphatic hydrocarbons and PAHs. The total petroleum hydrocarbon contents of sediments were relatively low or moderate compared to world-wide locations reported to be chronically contaminated by oil. On the whole, the degree of petroleum contamination in the Core Area and Buffer Area in YRDNNR is weaker than that of the Experimental Area. The potential ecosystem risk assessment indicated that PAHs will not cause immediate adverse biological effects in the YRDNNR. Besides oil-related hydrocarbon inputs in this region, aliphatic hydrocarbon analysis showed the presence of hydrocarbons of terrestrial origin at some sampling sites, characterized by high CPI values. Based on PAH ratios and principal component analysis, pyrolytic input may be a major source of PAHs in YRDNNR sediment, while petrogenic inputs were more apparent at some sites in the Experimental Area due to oil exploration in the Shengli Oilfield.     

Black carbon in soils from different land use areas of Shanghai,China: Level,sources and relationship with polycyclic aromatic hydrocarbons

Black carbon (BC) in soils plays a key role of carrying hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs). However, little is known about the spatial distribution, sources of BC and its relationship with PAHs in urban soils. We studied BC, total organic carbon (TOC) and PAHs concurrently in 77 soils collected from downtown area, suburban and rural area and industrial area of Shanghai, China. BC was determined by both chemical oxidation (dichromate oxidation, BC_Cr) and chemo-thermal oxidation (CTO-375, BC_CTO). BC sources were identified qualitatively by BC/TOC concentration ratios and BC-cogenerated high molecular weight (HMW) PAH isomer ratios and quantitatively by principal component analysis followed by multiple linear regression (PCA-MLR). Results showed that BC_Cr concentration (4.65 g/kg on average) was significantly higher than BC_CTO (1.91 g/kg on average) in Shanghai soils. BC_Cr concentrations in industrial area were significantly higher than those in other two. Stronger correlation was found between PAHs and TOC, BC_Cr than that between PAHs and BC_CTO, which indicates the possibility of PAHs being carried by charcoal and other organic matters thus negating its exclusive dependence on soot. Charcoal was therefore suggested to be taken into account in studies of BC and its sorption of PAHs. BC/TOC ratios showed a mixed source of biomass burning and fossil fuel combustion. PCA scores of BC-cogenerated HMW PAHs isomer ratios in potential sources and soil samples clearly demonstrated that sources of BC in urban soils may fall into two categories: coal and biomass combustion, and traffic (oil combustion and tire wear). PCA-MLR of HMW PAHs concentrations in soil samples indicated that coal and oil combustion had the largest contribution to BC in urban soils while tire wear and biomass combustion were important in downtown and rural area, respectively, which indicated they were main sources of HMW PAHs and presumably of BC.     

广州市空气颗粒物中烃类物质的粒径分布

用 Andersen六段分级大流量采样器 (粒径为 : 10～ 7.2 μ m, 7.2～ 3.0 μ m, 3.0～ 1.5 μ m, 1.5～ 0.95 μ m, 0.95～ 0.49 μ m, ≤ 0.49 μ m)采集了广州市荔湾区 4个季度的大气颗粒物样品 , 用气相色谱 (GC)定量分析了其中的正构烷烃 (n-alkanes)组分,用气相色谱-质谱 (GC-MS)定量分析了其中的多环芳烃 (PAHs)组分. CPI2(代表石油成因的碳优势指数 )、 CPI3(代表生物成因的碳优势指数 ) 和 Wax(植物蜡含量 )表明了石油成因的烷烃倾向于富集在细颗粒物上,而生物成因的烷烃倾向于富集在粗颗粒物上.正构烷烃和低相对分子质量多环芳烃表现出双峰模型分布,高相对分子质量多环芳烃呈现单峰模型分布,仅在细颗粒段有一峰值.烷烃和芳烃秋冬季的 MMDs(质量中值直径 )比春夏季的大.在高温季节化合物优先富集在细颗粒物上,而在低温季节则向粗的颗粒物方向偏移.     

Source identification of polycyclic aromatic hydrocarbons in sediments of a creek around a flow station

Sources of the sixteen polycyclic aromatic hydrocarbons (PAHs) in the United States Environmental Protection Agency priority pollutants list were determined in sediments of Kolo Creek using diagnostic ratios of parent PAHs[phenanthrene/phenanthrene + anthracene; fluoranthene/fluoranthene + pyrene; benz(a) anthracene/benz(a) anthracene + chrysene and indeno(1,2,3-d)pyrene/indeno(1,2,3-cd)pyrene + benzo(ghi)pyrelene]. The study was conducted over four seasons (dry, late dry, rainy and late rainy seasons). Applying cross plots of the diagnostic ratios revealed that PAHs in Kolo Creek sediment have pyrogenic origins except in the rainy season that had petrogenic origins. Comparison of diagnostic ratio values obtained from this study with literature values enabled the further classification into types of pyrogenic and/or petrogenic sources. While the pyrogenic sources of PAHs were mainly as a result of Grass/Wood combustion, the petrogenic PAHs were as result of drained diesel and lubricating oil. The predicted sources corresponded with the prevailing human activities in the vicinity, especially samples collected near a petrol station and an abattoir. This study further affirms the simplicity and accuracy of the use of diagnostic ratios for PAHs source prediction.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons in finegrained sediments of the East China Sea

The nearshore mud area along the Changjiang （Yangtze River） estuary and the coast of Zhejiang and Fujian provinces, and the distal mud area to the southeast of Cheju Island, Korea are the modem accumulative centers, thus, being the ＂sinks＂ of pollutants such as Polycyclic Aromatic Hydrocarbons （PAHs） in the East China Sea （ECS）. PAHs of surface sediment samples from the mud areas of the ECS and a ^210Pb dating sediment core collected using a gravity core from the coastal mud area in the ECS were quantified by GC/MSD with the internal standard materials.     

Flux of nutrients and heavy metals from the Melai River sub-catchment into Lake Chini, Pekan, Pahang, Malaysia

This study was carried out to determine the flux of nutrients and heavy metals from the Melai sub-catchment into Lake Chini through the process of erosion. Melai River is one of the seven feeder rivers that contributed to the present water level of Lake Chini. Three properties of soils, such as particle size, organic matter content, and soil hydraulic conductivity and three chemical soil properties, such as available nutrients, dissolved nutrients, and heavy metals, were analyzed and interpreted. Potential soil loss was estimated using the revised universal soil loss equation model. The results show that the soil textures in the study area consist of clay, silty clay, clay loam, and sandy silt loam. The organic matter content ranges from 3.40 to 9.92 %, while the hydraulic conductivity ranges from 5.2 to 25.3 cm/h. Mean values of available P, K, and Mg amount was 8.5 ± 3.7 μg/g, 24.5 ± 3.4 μg/g, and 20.7 ± 18.6 μg/g, respectively. The highest concentration of soluble nutrients was SO ₄ ^?2 (815.8 ± 624.1 μg/g), followed by NO₃ ^?-N (295.5 ± 372.7 μg/g), NH₄ ⁺-N (24.5 ± 22.1 μg/g) and PO₄ ^3? (2.0 ± 0.8 μg/g). The rainfall erosivity value was 1658.7 MJ mm/ha/h/year. The soil erodibility and slope factor ranges from 0.06 to 0.26 ton h/MJ/mm and 7.63 to 18.33, respectively. The rate of soil loss from the Melai sub-catchment in the present condition is very low (0.0028 ton/ha/year) to low (18.93 ton/ha/year), and low level flow of nutrients and heavy metals, indicating that the Melai River was not the contaminant source of sediments, nutrients, and heavy metals to the lake.