Atmospheric wet deposition of PAHs to the sea-surface microlayer

Sea-surface microlayer (SML) and subsurface seawater samples (SSW) collected from Singapore's coastal environment were analyzed for 14 polycyclic aromatic hydrocarbons (PAHs) in the dissolved (DP) and suspended particulate phase (SPM). Samples were collected prior to and after rainfall events to ascertain the contribution of wet atmospheric deposition of PAH enrichment to the SML. The concentration ranges of summation operatorPAHs in the SML before rain and after wet deposition were 2.6-46.2 ngL(-1) and 4.3-278.0 ngL(-1), respectively, for the DP and 3.8-31.4 ngL(-1) and 12.8-1280 ngL(-1), respectively, for the SPM. Load factors (i.e. concentration after wet deposition relative to before wet deposition) of the atmospheric wet deposition for DP and SPM ranged from 1.4 to 42.9 and 1.2 to 337, respectively. This study provides the first data on PAH concentration, enrichment (i.e. concentration of PAHs in SML relative to subsurface water) and load factors in the SML before and after wet deposition to the ocean surface.     

小白洋淀水-沉积物系统多环芳烃的分布、来源与生态风险

以端村小白洋淀为研究对象,利用GC-MS测定了6个样点水、悬浮物和沉积物中15种优控多环芳烃(PAHs)的含量,分析了其组成与来源特征,探讨了不同多环芳烃单体的生态风险,结果表明:(1)15种优控多环芳烃的总含量(PAH15),水相为40.1-74.0ng/L,算术均值51.0ng/L;悬浮物为2438.0-5927.0ng/g,算术均值4528ng/g;沉积物为466.9-1366.4ng/g,算术均值为755.6ng/g;与国内外有关研究相比,污染较轻,(2)三相中均以2、3环PAHs为主,其比例均高于80%;并且,从水相、悬浮物相到沉积物相,2环PAHs依次降低,3环、4环依次升高,高环检出率和含量也依次升高,(3)沉积物中多环芳烃的来源以生物质燃料(秸秆、薪材)和煤的燃烧为主,以液体化石燃料(汽油、柴油和原油)的燃烧为辅,(4)沉积物中的芴(FLO)、菲(PHE)含量在潜在生态风险效应区间低值(ERL)与中值(ERM)之间,其生态风险几率介于10%-50%之间;其他PAHs单体的含量均低于ERL,其生态风险几率均低于10%.     

Occurrence and phase distribution of polycyclic aromatic hydrocarbons in riverine runoff of the Pearl River Delta, China

The occurrence and phase distribution of polycyclic aromatic hydrocarbons (PAHs) in waters at the eight riverine outlets of the Pearl River Delta (China) were examined based on a monthly sampling program from March 2005 to February 2006. The total concentrations of PAHs in the aqueous phase and suspended particulate matter (SPM) combined ranged from 55.5 to 522 ng/L, at the mid level of the global values in rivers and estuaries. No clear temporal and spatial trends of PAH concentrations were found. However, the concentrations of PAHs associated with SPM coincided with the monthly precipitation of Guangzhou, indicating the importance of atmospheric deposition. The PAHs found in the region were likely derived from a combined pyrolytic and petrogenic origin, as suggested by the molecular indices of PAHs. Normalized partition coefficient (K(oc)) between water and SPM was correlated with octanol-water partition coefficient (K(ow)) to understand the environmental behavior of PAHs.     

Occurrence and phase distribution of polycyclic aromatic hydrocarbons in riverine runoff of the Pearl River Delta,China

The occurrence and phase distribution of polycyclic aromatic hydrocarbons (PAHs) in waters at the eight riverine outlets of the Pearl River Delta (China) were examined based on a monthly sampling program from March 2005 to February 2006. The total concentrations of PAHs in the aqueous phase and suspended particulate matter (SPM) combined ranged from 55.5 to 522 ng/L, at the mid level of the global values in rivers and estuaries. No clear temporal and spatial trends of PAH concentrations were found. However, the concentrations of PAHs associated with SPM coincided with the monthly precipitation of Guangzhou, indicating the importance of atmospheric deposition. The PAHs found in the region were likely derived from a combined pyrolytic and petrogenic origin, as suggested by the molecular indices of PAHs. Normalized partition coefficient (K_oc) between water and SPM was correlated with octanol–water partition coefficient (K_ow) to understand the environmental behavior of PAHs.     

Distributions of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China)

The distributions of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the aqueous phase, suspended particulate matter (SPM), sediment, and pore water of the Daliao River Estuary in Liaodong Bay, Bohai Sea (China). Total PAH concentrations ranged from 139.16 to 1717.87 ng L⁻¹ in surface water, from 226.57 to 1404.85 ng L⁻¹ dry weight in SPM, from 276.26 to 1606.89 ng g⁻¹ dry weight in sediments, and from 10.20 to 47.27 μg L⁻¹ in pore water. PAH concentrations were at relatively moderate levels in water, SPM, sediment and pore water in comparison with those reported for other estuary and marine systems around the world. Sedimentary PAH concentrations decreased offshore owing to active deposition of laterally-transported river-borne particles. PCA analysis of the possible PAH source suggested petrogenic and pyrolytic PAH inputs in the studied region.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait, China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24-25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L(-1), and 10.3-45.5 ng L(-1), which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

Enrichment and partitioning of polycyclic aromatic hydrocarbons in the sea surface microlayer and subsurface water along the coast of Xiamen Island,China

Sea microlayer (SML) and subsurface water (SSW) samples were collected around Xiamen Island to study the enrichment and partitioning of polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 93.43 to 411.05 ng L⁻¹ in the SML and 49.29–279.42 ng L⁻¹ in the SSW. Compared with the results of previous studies before pollution control measurements, PAHs levels decreased significantly. The enrichment factors (EFs) of dissolved and particulate PAHs varied from 0.68 to 2.71 and 0.43–3.56. EFs showed the consistent enrichment trends with sites and exhibited different enrichment characteristics between 2 and 3 ring PAHs and 4 ring PAHs. Furthermore, the much higher concentrations of BaP (strong carcinogenicity) were accompanied by higher EFs in the SML samples from the Western Xiamen Harbour, which together indicated the risk of impacts to the fish eggs that usually float on the SML water after exposure to oil spills and combustion, contributed directly by the port and shipping activities.     

Distribution of organochlorines in the dissolved and suspended phase of the sea-surface microlayer and seawater in Hong Kong, China

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were measured in the dissolved and suspended particulate phase in the sea-surface microlayer (SML) and subsurface water (SSW) collected from Hong Kong's coastal environment. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in the SSW dissolved phase (DP i.e. sum of truly dissolved and colloidal phase) were 409-940 (mean 602), 774-5583 (mean 1908) and 266-433 (mean 278), respectively. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in SSW suspended particulate matter (SPM) were <5-85 (mean 59), 358-1369 (mean 787) and 85.6-273 (mean 172), respectively. The enrichment factor of PCBs and OCPs in the SML varied between 1.1 and 4.5 for the DP, and 0.4-8.2 for the SPM. The distribution of contaminants between DP and SPM in both the SML and SSW indicates that particulate matter plays an important role in the distribution and fate of DDTs and PCBs, but not for HCH isomers. The Pearl River Estuary is likely to be a major source of contaminants transported to Hong Kong.     

The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea)

A field operable surface enhanced Raman scattering (SERS) sensor system was applied for the first time under real conditions for the detection of polycyclic aromatic hydrocarbons (PAHs) as markers for petroleum hydrocarbons in the Gulf of Gdańsk (Baltic Sea). At six stations, seawater samples were taken, and the sensor system was applied in situ simultaneously. These measurements were compared to the results of conventional GC/MS laboratory analysis of the PAH concentrations in the seawater samples. For a PAH concentration above 150 ng(12PAH)l(-1), there was agreement between the SERS sensor and the GC/MS determinations. A standard addition experiment yielded a PAH concentration of 900 ng l(-1) at the Gdańsk Harbor, which was of the same order as the GC/MS determinations of 12PAHs (200 ng(12PAH)l(-1)). The high SERS detection limit for seawater samples is explained by the competition for PAHs between the sensor membrane and particulate matter surfaces. Thus, the SERS sensor can be applied, e.g., as a non-quantitative alarm sensor for relatively high PAH concentrations in heavily polluted waters. The spectral unmixing procedure applied for Gdańsk Harbor water confirmed the presence of phenanthrene at the highest concentration ([Phe]=140 ngl(-1)) and of Chr (2.7 ng l(-1)), but it did not detect the other PAHs present in the Gdańsk Harbor water, as determined by GC/MS. When compared to the past literature and databases, the SERS spectra indicated the presence of a mixture of molecules consisting of carotenoids, n-alkanes, amines or fatty acids, and benzimidazoles at the coastal station ZN2. The spectra in the offshore direction indicated carboxylic acids. Interpretation of the farthest offshore in situ SERS measurements is difficult, principally due to the limited availability of reference spectra. The detection of the lower PAH concentrations commonly found in Baltic coastal water needs further research and development to obtain better sensitivity of the SERS sensor. However, the high analytical specificity of the SERS sensor also allows the detection of other chemical species that require the development of a SERS/Raman library for specific in situ spectral interpretation.     

Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS)

The laboratory characterization of a field-operable surface-enhanced Raman scattering sensor (SERS optode) is presented for the detection of aromatic hydrocarbons in seawater. The sensor has been developed for deployment with a robust underwater spectrograph. To meet the demands of the harsh seawater application, sol-gel derived SERS substrates were used. The calibration curves of six PAHs were determined to be of Langmuir adsorption isotherm type with limits of detection ranging from the microg l(-1) to ng l(-1) level. The experimentally determined adsorption constants varied strongly with the molecular weight of the analytes and correlated with their solubility. A mixture of five PAHs dissolved in seawater was investigated to demonstrate the utility of this method for screening. Emphasis was put on the interference from suspended particulate matter (SPM). The Raman measurement with backscattering configuration was shown to be immune against turbidities up to 1000 NTU. The physico-chemical interference arising from adsorption by the sediment was measured on-line by adding sediment to a PAH-spiked solution. According to the calibration curve, the PAH concentration decrease corresponded to more than 98% of the analyte being scavenged by the sediment.     

The Consequences of the Oder Flood in 1997 on the Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in the Oder River Estuary

Changes in the levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) as a consequence of the Oder flood in the summer of 1997 were investigated in surface water samples and fluffy layer material from the Oder Lagoon and the Pomeranian Bight. The measurements of the contaminants were complemented by satellite data to describe the spreading of the Oder flood discharge including the distribution of the particulate material. During the flood elevated levels of PAHs were discussed in the surface water and fluffy layer material of the Oder River Estuary in comparison to the average values in this region. These increased concentrations were attributed to flooding of municipal and industrial waste disposal areas in the drainage area of the Oder River. The meteorological conditions during the sampling period were characterized by predominant easterly winds, which guided the river plume along the German coast into the Arkona Sea, as verified by satellite observations. The highest concentrations of PAHs were observed near the mouth of the Swina and along the main direction of the river plume. Elevated concentrations of PAHs were also found in fluffy layer samples taken from the Oder Lagoon in late August. As derived from satellite data the eastern and the western parts of the lagoon differed in their SPM load during the entire flood period. The eastern part was covered by Oder water, while the western part contained a mixture of Oder Lagoon water. The highest concentrations of PAHs were not observed in the western part with the highest suspended matter values, but in the eastern part where the flood water entered the lagoon. Despite the significantly increased PAH levels measured during the flood, all measured concentrations were below the values that are considered to pose a risk to the ecosystem.     

Trace contaminant concentrations in the Kara Sea and its adjacent rivers, Russia.

Trace organic (chlorinated pesticides, PCBs, PAHs and dioxins/furans) and trace metal concentrations were measured in surficial sediment and biological tissues (i.e., worms, crustaceans, bivalve molluscs, and fish livers) collected from the Russian Arctic. Total DDT, chlordane, PCB and PAH concentrations ranged from ND to 1.2, ND to <0.1, ND to 1.5 and <20-810 ng g(-1), respectively, in a suite of 40 surficial sediment samples from the Kara Sea and the adjacent Ob and Yenisey Rivers. High sedimentary concentrations of contaminants were found in the lower part of the Yenisey River below the salt wedge. Total dioxins/furans were analysed in a subset of 20 sediment samples and ranged from 1.4 to 410 pg g(-1). The highest trace organic contaminant concentrations were found in organisms, particularly fish livers. Concentrations as high as 89 ng g(-1) chlordane; 1010 ng g(-1) total DDTs; 460 ng g(-1) total PCBs; and 1110 ng g(-1) total PAH, were detected. A subset of 11 tissue samples was analysed for dioxins and furans with total concentrations ranging from 12 to 61 pg g(-1). Concentrations of many trace organic and metal contaminants in the Kara Sea appear to originate from riverine sources and atmospheric transport from more temperate areas. Most organic contaminant concentrations in sediments were low; however, contaminants are being concentrated in organisms and may pose a health hazard for inhabitants of coastal villages.     

Polycyclic aromatic hydrocarbons (PAHs) in the mariculture zones of China’s northern Yellow Sea

Polycyclic aromatic hydrocarbons (PAHs) were detected in water and sediment samples collected from three mariculture zones in China’s northern Yellow Sea. In these samples, total PAH concentrations ranged from 110.8 ng/L to 997.2 ng/L and 142.2 ng/g dry weight (dw) to 750.2 ng/g dw, respectively. The log K_OC values of the various PAH compounds examined in this study increased with the log K_OW values, which is consistent with the prediction regarding PAH behavior in the environment. However, these K_OC values were lower than the predicted values as a result of the effects of organic matters, which were abundant in the mariculture water. The isomeric ratios of the PAHs in sediment indicated that the source of the PAHs in the mariculture zones were mainly pyrolytic. The TEQ^carc values of PAHs ranged from 7 ng TEQ/g dw to 92 ng TEQ/g dw, and only a few samples met the safe criterion with respect to individual PAH concentrations.     

Sources and geochemical constraints of polycyclic aromatic hydrocarbons (PAHs) in sediments and mussels of two Northern Irish Sea-loughs.

Polycyclic aromatic hydrocarbons (PAHs) were sampled from 30 sediment and 8 mussel (Mytilus edulis) stations in two Northern Irish Sea-toughs. Analysis was performed by gas chromatography coupled to mass spectrometry (GC-MS). Sedimentary organic carbon, % silt/clay and mean grain size were analysed in order to assess the role of geochemistry on PAH distribution. With the exception of two sites in Larne Lough representing localized regions of high contamination, sum(PAHs) in sediments ranged between 83 and 2300 ng g(-1). Regression analysis indicated that particle size and organic C were dominant factors in controlling the distribution of PAHs throughout the sediments. Sources of PAHs in both sea-loughs were dominated by pyrogenic inputs suggesting that diffuse sources such as atmospheric deposition may be a major source to both water bodies. The sum of PAHs in mussels ranged between 95 and 184 ng g(-1). Variations in concentrations may be explained by differences in the condition between mussel populations. Mussels in both sea-loughs exhibit similar metabolic activities towards the PAH compounds which were predominantly bioaccumulated from sediments.     

Polycyclic aromatic hydrocarbons in surface sediments of the East China Sea and their relationship with carbonaceous materials

This study measured concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface sediments in the East China Sea (ECS) to investigate possible sources and fate of PAHs. Total concentration of PAHs in the sediments of the ECS ranged from 22 to 244 ng g(-1), with the highest levels in the coastal area and outer shelf. The observed PAH results showed elevated levels in both inner and outer shelf areas, a finding that is different from predictions by an ocean circulation model, suggesting that terrestrial sources are important for PAH contaminations in the ECS, while sediment resuspension, tidal changes and lateral transport may be important in affecting the distribution of PAHs in the outer shelf. The distribution of PAHs in the surface sediments of the ECS is similar to the distribution of carbonaceous materials (e.g., particulate organic carbon and black carbon), suggesting that carbonaceous materials may strongly affect the distribution of PAHs.     

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides in water columns from the Pearl River and the Macao harbor in the Pearl River Delta in South China

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) were measured in suspended particles and dissolved phase from the Baiertang water column and the Macao water column samples as collected from the Guangzhou channel of the Pearl River and the Macao harbor, where the sediments were heavily contaminated with organic pollutants. Total OCPs concentration varies from 23.4 to 61.7 ng/l in Baiertang water column and from 25.2 to 67.8 ng/l in Macao column, while total PAHs concentration varies from 987.1 to 2878.5 ng/l in the Baiertang water column and from 944.0 to 6654.6 ng/l in the Macao column. The vertical distribution profiles of pollutants and the partition of pollutants between particles and dissolved phases indicate that the sediments in Baiertang act as an important source of selected pollutants, and the pollutants in water of this region were mainly originated from the release and re-suspension of contaminants residing in the sediments. The sediments in Macao harbor act as a reservoir for organochlorine pesticides, such as DDTs mainly introduced by river inflow from Xijiang and PAHs input by brackish water from the Lingdingyang estuary. Combustion of fossil fuels and petroleum input are the main sources of PAHs in the Macao water column, while combustion of fossil fuels and coal is responsible for the PAHs in the Baiertang water column. The ratios of DDT/(DDD+DDE) for the Macao water column samples demonstrate that such chemicals were input into this region in recent times.     

PAH-profiles in sediment cores from the Baltic Sea

To document the historical input the PAH-profiles of sediment cores in two different basins of the Baltic Sea, the Gotland Basin (GB) and Arkona Basin (AB), were analysed by means of GC-MS. 35 PAHs were quantified in all samples, and additionally, several marker PAHs, like Cyclopenta[cd]phenanthrene (CCP) for combustion processes and retene for terrigenous input, were quantified in selected samples. The preindustrial sediments (older than 200-250 years) in the GB core illustrate concentrations <100 ng PAH15 g(-1) d.w. Calculated PAH-ratios indicated combustion processes as the main sources for both basins. The Perylene concentrations within the sediment cores decrease with increasing depth, along with an increase in relative percentage, indicating slow diagenetic processes. The preservation and enrichment of the introduced PAHs was more pronounced in the GB core.     

Mechanisms controlling the intra-annual mesoscale variability of SST and SPM in the southern North Sea

Thermal and optical remote sensing data were used to investigate the spatial and temporal distribution of sea surface temperature (SST) and of suspended particulate matter (SPM) in the southern North Sea. Monthly SST composites showed pronounced seasonal warming of the southern North Sea and delineated the English coastal and continental coastal waters. The East-Anglia Plume is the dominant feature of the English coastal waters in the winter and autumn SPM composites, and the Rhine region of freshwater influence (ROFI), including the Flemish Banks, is the dominant feature of the continental waters. These mesoscale spatial structures are also influenced by the evolution of fronts, such as the seasonal front separating well-mixed water in the southern Bight, from the seasonally stratified central North Sea waters. A harmonic analysis of the SST and SPM images showed pronounced seasonal variability, as well as spring-neap variations in the level of tidal mixing in the East Anglia Plume, the Rhine ROFI and central North Sea. The harmonic analysis indicates the important role played by the local meteorology and tides in governing the SST and near-surface SPM concentrations in the southern North Sea. In the summer, thermal stratification affects the visibility of SPM to satellite sensors in the waters to the north of the Flamborough and Frisian Fronts. Haline stratification plays an important role in the visibility of SPM in the Rhine ROFI throughout the year. When stratified, both regions typically exhibit low surface SPM values. A numerical model study, together with the harmonic analysis, highlights the importance of tides and waves in controlling the stratification in the southern North Sea and hence the visibility of SPM.     

Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan

Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g(-1) dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQcarc) of PAHs varied from 55 to 1964 ng TEQ g(-1) dry weight. Higher total TEQcarc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g(-1) dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects.     

DDT, PAH and PCB in sediments from the intertidal zone of the Bohai Sea and the Yellow Sea

Current contents of persistent organic contaminants, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and the congeners (naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(a)pyrene and benzo(e)pyrene), DDTs and metabolites in the intertidal sediments of the Bohai Sea and the Yellow Sea were studied. The mean levels of DDTs, PAHs and PCBs were 177.52, 877.2 and 3.4 ng g-1 dry weight, respectively. The spatial trends of the contaminant residue levels were analysed too.