Sources and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay)

This contribution characterises the sources and distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Basque coast (Bay of Biscay). Different source characterisation approaches (i.e. GIS assisted-chemometrics, PAH diagnostic ratios and analyses of composition profiles) were used in combination to successfully identify the factors determining the origin and distribution of PAHs. Urban/industrial combustion processes were identified as the main PAH source. However, the analysis of PAH composition patterns and diagnostic ratios identified secondary natural and petrogenic PAH sources on small spatial scales. The median ∑18PAH concentration ranged from 66 μg kg^?1 (d.w.) to 7021 μg kg^?1 (d.w.). The Ibaizabal estuary, which supports most of the anthropogenic pressure in the region (i.e. urban development, industrialisation, commercial and recreational harbours), also showed the highest PAH concentrations. On the shelf, human activities, hydrodynamic conditions and geomorphological features led to spatial differences in the PAH concentrations among sectors: the offshore and west sectors were characterised by higher concentrations, while the lowest values were found in the mid and east sectors. The results enhance the knowledge on PAH-related contamination processes and could be used to support the environmental assessment process required under current European marine legislation.     

Monitoring the effectiveness of the European tributyltin regulation on the Basque coast (northern Spain) by assessing imposex in two gastropod species (Nassarius reticulatus and Nassarius nitidus)

Imposex and butyltin body burden were assessed in 2011 along the Basque coast (northern Spain) in two gastropod species (Nassarius reticulatus and Nassarius nitidus) four years after an initial survey in 2007. The aim of this re-survey was to monitor the effectiveness of the European ban on the use of tributyltin (TBT) based antifouling paints on ships’ hulls (EC 782/2003). Imposex levels in 2011 were lower than those determined in 2007 at most of the sampling sites. Accordingly, TBT concentrations in the female body burden of Nassarius reticulatus varied from 43 to 250 ng Sn/g in dry weight in 2011, which was a lower maximum than in 2007. Nevertheless, the results for the butyltin degradation index suggest that there have been recent inputs of TBT within the two main Basque harbours. Overall, the legislative measure is contributing to the reduction of TBT effects on the Basque coast although its presence is still evident.     

环渤海北部沿海地区表层土壤中PAHs的污染特征及风险评价

系统采集了环渤海北部沿海地区31个表层土壤样品,利用GC/MS分析了16种USEPA优控多环芳烃(PAHs)的含量和组分特征,运用主成分因子载荷法揭示了其污染来源,并初步评价了其风险水平.结果表明,沿海地区65%的土壤已被污染,最高污染样点PAHs含量达920.4ng·g-1,平均含量309.5ng·g-1,与国内外相关研究比较,处于中低等污染水平.各类燃料的不完全燃烧是该地区土壤中PAHs的主要来源,石油类挥发或泄漏对采油区土壤中PAHs的累积影响显著.     

Determination of polychlorinated biphenyl and polycyclic aromatic hydrocarbon marine regional Sediment Quality Guidelines within the European Water Framework Directive

Marine regional Sediment Quality Guidelines (SQG) for polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) from the Basque coast (SE Bay of Biscay) were determined, on the basis of sediment chemistry, toxicity and benthic community disturbance from analysis of 756 estuarine and coastal samples. The SQG were calculated using a percentile approach (based upon effect and non-effect data), using non-normalised and normalised concentration, by total organic carbon. However, normalisation by total organic carbon did not result in any improvement in accuracy compared with non-normalised values. Hence, this study proposes non-normalised SQG values for assessment of the chemical and physicochemical status in marine waters in the Basque Country, within the Water Framework Directive: 24.6–29 μg kg^?1 for total PCBs; 164–285 μg kg^?1 for low molecular weight PAH; 922–1537 μg kg^?1 for high molecular weight PAH; and 1607–2617 μg kg^?1 for total PAH.     

Vertical distribution and environmental significance of PAHs in soil profiles in Beijing,China

Vertical distribution of both the concentration and composition of polycyclic aromatic hydrocarbons (PAHs) in ten profiles in Beijing has been investigated. The results showed that PAH concentrations and compositions in topsoil from different sampling sites were different. PAH concentrations were much higher in topsoil of the investigated urban area, industrial region, and paddy field with wastewater irrigation than in other areas. Moreover, PAH concentrations in topsoil were much higher than those at greater depth, where the concentrations were relatively consistent in most soil profiles. The fingerprints of PAHs in the samples from topsoil (0–30 cm) in the same profiles were similar and were obviously different from those at greater depth, suggesting that PAH sources were consistent in topsoil samples and were discriminating between topsoil and deeper soils. PAHs in topsoil mainly arose from mixed sources of combustion of liquid fuel, coal, and/or wood, as well as wastewater irrigation, while those at greater depth were derived from soil genesis and the process of soil formation.     

Sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Biobio River in south central Chile

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; there are concerns about them due to their toxic properties. Human activities could significantly contribute to the total PAH burden in river sediments. In this work, we document the analysis of PAHs in sediments taken in the middle stretch of the Biobio River in south central Chile. This river is a principal system, draining more than 24,000 km² and subjected to a diverse variety of human-made stressors (pulp mill and urban effluents, agricultural drainage systems, etc). During 2003, several sediment samples were taken in more than 45 sampling sites located in the river’s middle stretch. Due to the granulometric characteristics (mainly sandy sediments), only 17 samples were analyzed, taking into consideration the presence of a fine section within the sediment sample. Using HPLC with fluorescence detection, 15 EPA priority PAHs and perylene were analyzed. The composition of PAHs in the sediment samples is rather similar between sites and levels averaged 104 ± 78 ng g⁻¹ d.w. The highest levels were detected downstream from an industrial discharge. A good correlation was observed between PAH levels and organic carbon content in the tested sediments; however, concentrations above 134 ng g⁻¹ d.w. did not indicate correlation. The samples PAH ratios (Flu/Pyr and Chr/B(a)A) reveal a strong pyrolytic PAH pattern in the sediments tested, supporting evidence indicating that PAHs come mainly from pyrolytic sources. This result contrasts with previous records that have shown a natural influence in the upper basin and a petrogenic pattern near the mouth.     

Polycyclic aromatic hydrocarbons in soils around Guanting Reservoir,Beijing, China

The concentrations of 16 polycyclic aromatic hydrocarbons (∑ 16PAHs) were measured by gas chromatography equipped with a mass spectrometry detector (GC-MS) in 56 topsoil samples around Guanting Reservior (GTR), which is an important water source for Beijing. Low to medium levels of PAH contamination (mean=394.2±580.7 ng g^?1 dry weight (d.w.)) was evident throughout the region. In addition, localised areas of high PAH contamination near steel and cement factories were identified, with ∑ 16PAHs concentrations as high as 4110 ng/g, dry weight (d.w.). There was a significant positive correlation (r²=0.570, p<0.01) between total organic carbon content and ∑ 16PAHs concentrations. Phenanthrene was the predominant compound, accounting for 27.2% of the ∑ PAH concentration, followed by chrysene>pyrene>benzo[a]anthracene≈ benzo[b]fluoranthene≈ benzo[a]pyrene. Four-ring PAH homologues (39%) were dominant. The higher proportion of 4–6 ring homologues, molecular indices, and the spatial distribution of PAH indicated that industrial discharges, incineration of wastes and traffic discharges were the major sources of soil PAHs around the water reservoir.     

Characterization and sources of PAHs in an urban river system in Beijing,China

Water samples from 20 locations on rivers in the Tongzhou District of Beijing were collected four times from July 2005 to March 2006. In addition, sediment samples were collected in July 2005. All samples were analyzed for 16 US Environmental Protection Agency (EPA) priority pollutants polycyclic aromatic hydrocarbons (PAHs). The concentration, distribution, seasonal variation, and sources of the 16 PAH compounds identified in the water samples, suspended particles, and surface sediments were then evaluated. The concentrations of PAHs in the water and suspended particle and surface sediment samples ranged from 87.3 to 1,890 ng l⁻¹, 1,330 to 27,700 ng g⁻¹, and 156 to 8,650 ng g⁻¹, respectively. These results demonstrated that rivers in the Tongzhou District of Beijing had a high level of PAH pollution, especially in the suspended particles. The highest and lowest concentrations of PAHs in the water samples were observed in summer and spring. However, the seasonal variations in the concentration of PAHs in the suspended particles were more complicated. The dominant compounds in the water, suspended particle, and surface sediment samples were two-, three- and four-ring PAH compounds, respectively. Ratio analysis illustrated that fuel-burning was the primary source of PAHs in the study area. Gasoline, diesel, coal, and coke oven sources were identified and the contributions of the different fuel-burning sources were then calculated using factor analysis and multiple linear regression. These analyses revealed that coal combustion, gasoline combustion plus coke oven emission, and diesel combustion accounted for 38.8%, 38.5%, and 22.7% of the PAHs in suspended particles, respectively.     

Lichens to distinguish urban from industrial PAHs

This paper shows that lichens can be used as biomonitors to distinguish urban from industrial polycyclic aromatic hydrocarbons (PAHs). PAHs are atmospheric pollutants originating mainly from incomplete combustion of fuels in vehicles and industry. The occurrence of PAHs in air is a serious health issue in urban areas and industrial areas because some PAHs are carcinogenic. Biomonitoring PAHs with lichens is generally applied for quantification of PAHs. However, the precise sources of PAHs are not well known. Here we use lichen to trace the source of PAHs. PAHs were analyzed in Pyxine subcinerea Stirton, a lichen species collected from twelve sites which vary from urban and industrial to periurban forest area of Haridwar, in the foothills of the Indian Himalayas. Total PAH concentration ranged between 1.25 and 187.3 μg g⁻¹. Results indicate a clear distinction between urban and industrial PAHs profile, using principal component analysis. Lichen sampled from industrial sites exhibited higher concentrations of two-, five-, and six-ringed PAHs, up to 60% of total PAHs, while samples from urban sites were dominated by four-ringed PAHs, predominantly fluoranthene and acenaphthylene. Molecular ratios indicate that combustion was the dominant source of origin of PAHs in industrial area, while urban sites showed mixed origin of PAHs, both pyro- and petrogenic.     

济南市PM2.5中二次组分的时空变化特征及其影响因素

为分析济南市PM_2.5中二次组分的时空变化和影响因素,对济南市春季(2019年5月16—25日)、秋季(2019年10月15—24日)和冬季(2019年12月17—2020年1月16日)4个典型点位的PM_2.5样品进行连续采样,并测定了PM_2.5中水溶性离子、有机碳(OC)和元素碳(EC)的含量。结果表明:物流交通区的二次组分质量浓度最高(56.13μg·m^?3),钢铁工业区的二次组分浓度比城市市区高,但是二次组分占比较城市市区低,清洁对照点的浓度和占比最低;济南市4个功能区SO₄^2?和NO₃^?转化率均高于0.1,除清洁对照点外,城市市区、钢铁工业区和物流交通区的SO₄^2?转化率明显高于NO₃^?转化率;济南市春季、秋季和冬季的ρ(NO₃^?)/ρ(SO₄^2?)分别为0.67、2.57和1.98,春季PM_2.5浓度以固定源贡献为主,秋季和冬季以移动源贡献为主;运用ISORROPIA热力学模型分析了含水量和pH对二次组分生成的影响,含水量会随着污染增大而增大,酸度和含水量对二次无机组分的转化机理产生影响,酸度会抑制二次无机组分的生成,而含水量会促进二次组分的生成;后向轨迹聚类分析结果表明,占比最高的轨迹(29.2%)来自东北方向的滨州和东营,基于潜在源贡献因子(WPSCF)和浓度权重轨迹(WCWT)分析PM_2.5中二次组分质量浓度的潜在污染源区域,SO₄^2?的主要贡献源区在济南市区北部的济阳区和东北方向的滨州、东营等,NO₃^?和NH₄⁺的主要贡献源区在济南市区北方向的济阳区、东北方向的章丘区和南方向的莱芜区等。该研究结果可为中国北方城市细颗粒物进一步的治理和防控提供数据支撑和理论依据。     

Assessment of the effect of environmental pollution in a marina on caged mussels using chemical and genotoxic analysis

An integrated approach using the contamination levels and DNA damage in mussels (Mytilus galloprovincialis) was applied in order to assess the chemical contamination in a marina (Eastern coastline of Aegean Sea). Mussels, which were harvested from a reference site (Foca), were transplanted into a marina situated along the coast of Izmir Bay. The transplanted mussels were collected at the 14th, 30th and 60th day of the experimental period. Polycyclic aromatic hydrocarbon (PAH) levels (27–51?ng?g^?1?wet?weight) detected in the mussels were similar to the levels detected in other coastal areas of the Mediterranean Sea. The marina’s sediment was found to be contaminated with PAHs (∑PAH?=?25?µg?g^?1) of pyrolytic origin and may become a source of pollution and a threat to the marine environment. In order to assess the DNA damage, the haemolymph and gill cells of the mussels were used for the comet analysis and considered as an indicator of exposure to genotoxic chemicals including 16 PAH compounds and metals. The highest levels of DNA damage expressed as %Tail-DNA (%T-DNA) were observed at the end of the experiment (21.5% T-DNA). The correlation analyses conducted between 2-, 3-, 4-ring PAHs in mussels and %T-DNA in haemolymph and gill cells showed a significant positive correlation. This investigation confirmed that transplanted mussel can be a useful tool to determine PAH contamination in marinas.     

固定化毛霉对工业和农田污染土壤中多环芳烃的降解和生物有效性评价

为了探讨微生物修复不同类型多环芳烃污染土壤的可行性,应用固定化毛霉对多环芳烃污染工业土壤及农田土壤进行微生物修复,用羟丙基-β-环糊精(HPCD)提取模拟评价多环芳烃的微生物可利用性,并分析多环芳烃微生物降解和生物可利用性的相关关系.焦化厂污染土壤中多环芳烃的30 d降解率为77.6%,沈抚灌区污染土壤中多环芳烃的30 d降解率为54.2%,焦化厂土壤和污灌区农田土壤中多环芳烃降解差异明显.焦化厂土壤和污灌区土壤中多环芳烃的30 d降解量和多环芳烃的环糊精可提取量具有相关性,各环数多环芳烃的环糊精可提取量变化解释了焦化厂和污灌区土壤中多环芳烃降解的差异机制,说明可用环糊精提取量预测微生物降解土壤多环芳烃的情况.     

珠江三角洲地区水体表层沉积物中多环芳烃的来源、迁移及生态风险评价

检测了珠江三角洲河流及南海近海表层沉积物中25种多环芳烃的含量．其含量范围为138-6793ng·g-1．主成分分析/多元回归分析结果表明,珠江三角洲水体沉积物中多环芳烃来源主要有石油排放,煤、木柴等低温燃烧排放,机动车尾气排放及生物成因．其相对贡献分别为石油排放占36％、煤、木柴燃烧占27％、机动车尾气占25％,自然来源占12％．珠江、东江河流沉积物中多环芳烃主要来源于区域内工业和生活废物的直接排入和机动车尾气的近距离沉降．西江沉积物中多环芳烃大气沉降是主要输入途径．南海沉积物中多环芳烃河流输入是主要途径．在多环芳烃由河流向海洋的输送过程中,茈可以作为一个有效指标示踪河流输送的多环芳烃．风险评价表明,东江及珠江部分河段沉积物可能存在着对生物的潜在危害,其它区域多环芳烃的生态风险处于较低水平．     

Modeling toxic endpoints for improving human health risk assessment of polycyclic aromatic hydrocarbons – parent compounds and simple mixtures

Risk assessments for mixtures of polycyclic aromatic hydrocarbons (PAH) are problematic due to the lack of available potency and toxicity data on individual compounds and mixtures. This article examines the toxicity of parent compounds and designed mixtures of PAH in order to bridge the gap between component assessment and mixture assessment for this class of ubiquitous compounds. The objective for this study was to test seven parent PAH compounds and four PAH mixtures in a set of three bioassays to evaluate the toxicity of parent compound PAH and binary mixtures of PAH. PAH and mixtures were examined in the Salmonella/microsome mutagenicity assay, a Gap Junction Intercellular Communication assay, and the 7-ethoxyresorufin-O-deethylase assay. These assays were chosen for their ability to measure specific toxic endpoints related to the carcinogenic process (i.e. initiation, promotion, and progression). Two compounds similar in structure, benzo(a) pyrene (BAP) and benzanthracene, consistently produced positive results in all three bioassays. Conversely, a linear PAH, anthracene, produced negative results in all three bioassays. An antagonistic response was observed for the mixtures in all three bioassays. Chemical structure was important in explaining the observed responses. Using chemical structure–activity relationships with the steps of the carcinogenic process may be used to improve estimates of toxicity for compounds and mixtures for human health risk assessments.     

Concentrations and classification of HCHs and DDTs in soil from the lower reaches of the Jiulong River, China

Soil is an important source to other environmental media and organisms for organochlorine pesticides (OCPs) bioaccumulation. Twenty-four representative surface soil samples were collected from the lower reaches of the Jiulong River, China, in 2009. The concentrations of hexachlorocyclohexane isomers (HCHs) ranged from 0.38 to 39.52 ng·g^?1, with a mean value of 9.51 ng·g^?1. The concentrations of dichlorodiphenyltrichloroethanes (DDTs) and their metabolites were within the ranges of 0.94–700.99 ng·g^?1, with a mean value of 71.17 ng·g^?1. The concentrations of HCHs and DDTs in the soil were lower than the first grade level (50 ng·g^?1) of the Chinese Environmental Quality Standard (GB15618-1995). Hierarchical Cluster Analysis (HCA) and Pearson’s bivariate Correlations Analysis (PCA) were used to analyse the distribution and contamination levels of OCPs in this region. The results showed that DDTs were the major contaminants and there were no significant correlations between various OCPs concentrations and the total organic carbon (TOC) contents. A significant positive correlation was observed between HCHs and DDTs (p<0.01), which indicates that HCHs and DDTs may have similar sources and fate in the study area.     

Background metal levels determination in bivalves – quality assessment of the European Water Framework Directive

Background levels of metals (Ag, Cd, Cu, Cr, Hg, Ni, Pb and Zn) in biomonitors (Mytilus galloprovincialis mussels and Crassostrea gigas oysters), in estuarine waters within the Basque Country (south-east Bay of Biscay) are estimated using non-parametric statistical tools and data are presented graphically, with the aim of being used in assessing the ecological status, within the European Water Framework Directive (WFD). The basis for this study was the statistical analysis of data compiled from monitoring programmes undertaken along the Basque coast, between 1990 and 2008. For this analysis, a heuristic method was adapted and used. Results showed different metal background ranges throughout the year for both mussels and oysters. Values corresponding to the upper limit of the background range (i.e. value of the upper whisker of the box-plot) are proposed as the ‘high/good’ status boundary, according to the WFD.     

Assessment of PAHs in water and fish tissues from Great Bitter and El Temsah lakes,Suez Canal,as chemical markers of pollution sources

Sea water and fish tissue samples were collected from nine sampling stations from the Great Bitter and El Temsah lakes in the Suez Canal and analysed for polycyclic aromatic hydrocarbon (PAH). The compositions of PAH determined in the dissolved fraction of sea water were measured in order to use them as chemical markers for identifying different sources of PAH pollution in this region. PAHs determined in fish tissues were measured for comparison with human health standards as consumption. The total mean PAHs concentrations in the sea water samples ranged from 0.28 to 39.57 μg l^?1 with an overall mean of 10.78 and 12.38 μg l^?1 for El Temsah and Bitter Lakes water, respectively. Total PAHs fractions recorded in muscle tissues of all different Osteicthyes fishes collected from Great Bitter lakes ranged from 5.8 to 218.5 μg g^?1 with an overall mean of 57.98 μg g^?1 during all seasons. However, they ranged from 68 to 623 μg g^?1 with an overall mean of 87.69 μg g^?1 recorded in El Temsah lake during four seasons (2003–2004). Benzo(a)pyrene was the most dominant PAHs found in the sea water samples from both lakes with an average concentration of 3.8 μ g l^?1. Dibenzo(a,h)anthracene (DBA) was the most dominant PAHs recorded in fish samples. A maximum of 533 μg g^?1 of DBA was recorded in Dahbana sp. collected from Bitter lakes during January 2004. However, a maximum of 68.7 μ g g^?1 was recorded in Liza carinata species collected from El Temsah lake during July, 2004. The simultaneous occurrence of isomer ratios PHE/ANT<10 for all stations indicated that the major PAH input to water was from combustion of fossil fuel (pyrolytic source). The average ratios were 1.21 and 12.9 during winter (January 2004) and 4.3 and 8.63 during spring (April 2004) for all water samples of Great Bitter lakes and El Temsah lake, respectively. In addition, the present data demonstrate that PAHs from fossil fuel sources (MW<178) were the least significant source of PAHs in this region.     

Polycyclic aromatic hydrocarbons in medicinal plants from Syria

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (EPA PAHs) in 10 medicinal plants in different used parts of plant (leaves and flowers) have been determined. The analytical method consists of sample preparation by ultrasonic extraction with dichloromethane followed by silica gel clean-up. Subsequently, the analysis was carried out by reversed-phase high-performance liquid chromatography (HPLC) coupled to both ultraviolet and fluorescence detections in series to insure the detection of all 16 EPA PAHs. It was observed that the sum of the 16 PAHs (ΣPAHs) in the investigated medicinal plants ranged from 47 to 890 μg kg^–1 where the highest ΣPAHs was found in Sage plant sample. Light PAHs were dominants in all studied medicinal plants. The sum of eight genotoxic PAHs (ΣPAH8) have shown a better indicator of the degree of contamination with carcinogenic PAHs compared to benzo[a]pyrene in these products.     

Residues and sources of organochlorine pesticides in soils of elementary schools and communities in Wenchuan 5.12 Earthquake-affected areas

The disinfectants and pesticides extensively used after Wenchuan 5.12 Earthquake on May 12, 2008 (so-called Wenchuan 5.12 Earthquake), for epidemic prevention purpose can raise great concerns of environmental pollution and potential personal exposure. To investigate the soil pollution caused by the intensive application in earthquake-affected areas, surface soil samples from two elementary schools, two communities and two background areas were collected in Beichuan County and Dujiangyan City once per location in spring and in autumn in 2011 and then analyzed by gas chromatography/mass spectrometry for organochlorine pesticides (OCPs). The results showed serious soil pollution of hexachlorocyclohexanes (HCHs, 0.05–60.05 ng/g) and dichloro-diphenyl-trichloroethane (DDTs, 0.06–35.79 ng/g) in the study areas compared with Wolong Nature Reserve (0.03–0.81 ng/g for HCHs and 0.02–0.40 ng/g for DDTs). The concentrations of most OCPs in soil of Beichuan County (e.g., 0.10–60.05 ng/g for HCHs and 0.17–35.79 ng/g for DDTs) were much higher than those of Dujiangyan City (e.g., 0.05–20.58 ng/g for HCHs and 0.06–10.69 ng/g for DDTs). In Beichuan County, the highest concentrations of HCHs and DDTs were found in the elementary school. In Dujiangyan City, the highest concentrations of HCHs and DDTs were found in the elementary school and the community, respectively. The concentrations of HCHs and DDTs were generally higher in spring than those in autumn. The predominant species (γ-HCH in ∑HCHs and 4,4′-DDT in ∑DDTs) and specific ratios suggested new inputs of lindane and technical DDT in the study areas. Therefore, continuous soil monitoring and possible intervention would be recommended to minimize local residents’ exposure to these toxic chemicals.