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.     

Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05–0.41 and 0.04–4.3 μg l⁻¹ in the SSW, peaking up to 38 and 1366 μg l⁻¹ in the SML, respectively. Dissolved and particulate PAHs ranged 1.9–98 and 1.9–21 ng l⁻¹ in the SSW, amounting up 217 and 1597 ng l⁻¹ in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9–11.5 in the dissolved phase.     

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.     

PCBs and PAHs in sea-surface microlayer and sub-surface water samples of the Venice Lagoon (Italy)

Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are two classes of micropollutants intensively monitored and regulated due to their toxicity, persistency and wide diffusion. Their concentrations have been investigated in sea-microlayer (SML) and sub-surface water (SSW) samples collected at two sites of the Venice Lagoon, a fragile ecosystem highly influenced by industrial and anthropogenic emissions. The total sigmaPCB concentration varies from 0.45 ng/l to 2.1 ng/l in SSW while a clear enrichment is observed in the SML, where it ranges from 1.2 ng/l to 10.5 ng/l. The total sigmaPAH concentration shows marked differences between the two stations and varies from 12.4 ng/l to 266.8 ng/l in SSW; in SML it is more uniform and ranges from 19.6 ng/l to 178.9 ng/l. The enrichment factors are not larger than 1 for both pollutants in the 'dissolved' phase, while they are most significant for the 'particulate' phase (sigmaPCB: 5-9; sigmaPAH: 4-14).     

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.     

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.     

Evaluation of sampling devices for the determination of polycyclic aromatic hydrocarbons in surface microlayer coastal waters

The sea surface microlayer (SML) may play an important role on the transport and fate of persistent organic pollutants in the marine environment. In order to evaluate the appropriateness of a number of sampling devices for the analysis of 14 parent polycyclic aromatic hydrocarbons (3-5 aromatic rings), marine SML waters were sampled using a glass plate, a rotating drum/roller, a metal screen and a surface slick sampler. The underlying waters were also sampled for the determination of the corresponding enrichment factors (EF = [C](microlayer)/[C](underlying water)). The EFs were phase dependent, ranging from 1 to 3 for the dissolved phase and between 4 and 7 for the particulate phase. In order to better assess the performance of the different sampling methods, in terms of phase partitioning, the truly dissolved and colloidal phases were also estimated. Generally, no significant differences were found for the enrichment factors provided by the different methods, due to the observed large variability in concentrations that can be attributed to small-scale coastal processes. However, the metal screen is recommended as the most efficient sampling method for the study of PAHs taking into account the amount of water collected versus time.     

Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: estimate of Sarno River inputs

The polycyclic aromatic hydrocarbons (PAHs) pollution in the Sarno River and its environmental impact on the Gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) were estimated. The 16 PAHs identified by the USEPA as priority pollutants and perylene were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total PAHs concentrations ranged from 23.1 to 2670.4 ng L(-1) in water (sum of DP and SPM) and from 5.3 to 678.6 ng g(-1) in sediment samples. Source analysis revealed that PAHs mainly came from combustion process. Contaminant discharges of PAHs into the sea were calculated in about 8530 gd(-1) showing that this river should account as one of the main contribution sources of PAHs to the Tyrrhenian Sea.     

Chlorinated pesticides and PCBs in the sea-surface microlayer and seawater samples of Singapore

Sea-surface microlayer (SML) and seawater samples collected from Singapore's coastal marine environment were analyzed for selected chlorinated pesticides and polychlorinated biphenyls (PCBs). The SML is a potential site of enrichment of persistent organic pollutants (POPs) compared to the underlying water column. The concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB in subsurface (1 m depth) seawater were 0.4-27.2 ng/l (mean 4.0 ng/l), 0.01-0.6 ng/l (mean 0.1 ng/l) and 0.05-1.8 ng/l (mean 0.5 ng/l) respectively. In the SML, the concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB were 0.6-64.6 ng/l (mean 9.9 ng/l), 0.01-0.7 ng/l (mean 0.2 ng/l) and 0.07-12.4 ng/l (mean 1.3 ng/l) respectively. High spatial and temporal distribution was observed for all POPs measured. However, overall levels measured in the SML were lower than levels reported in the literature for SML samples from temperate coastal regions-possibly due to loss of semi-volatile compounds in the tropical climate of Singapore. Atmospheric wet deposition during the monsoon season may be an important source of POPs to the SML. This study provides the first scientific data on POP concentrations and enrichment factors in the SML for Southeast Asia.     

Poly-aromatic hydrocarbon (PAH) inputs from the Rhône River to the Mediterranean Sea in relation with the hydrological cycle: impact of floods

The concentrations of dissolved and particulate polycyclic aromatic hydrocarbons (PAHs) were monitored in waters of the Rhône River (France) every fortnight for a full calendar year, from June 1994 to May 1995. All flood events occurring over the course of the experiment were sampled at higher frequency to better quantify the impact of these extreme hydrological episodes on the annual export of PAHs to the Mediterranean Sea. This time-series indicates that more than 90% of the annual load of particulate PAHs is transported during flood episodes, with 77% discharged during the course of only one extreme flood event occurring in November 1994. During these intense events, riverine particles are depleted in PAHs while at low river discharge particles are PAH-enriched. Dissolved PAHs were less variable and less abundant than adsorbed PAHs, consistently with the low solubility of these compounds.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

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.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.     

In-situ partitioning and bioconcentration of polycyclic aromatic hydrocarbons among water,suspended particulate matter,and fish in the Dongjiang and Pearl Rivers and the Pearl River Estuary,China

The partitioning and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in water, suspended particulate matter (SPM), and fish samples from the Dongjiang River (DR), Pearl River (PR), and the Pearl River Estuary (PRE) were examined. Although PAHs are much lower in PRE than in DR or PR, PAHs in some fish species are significantly higher in PRE than in DR or PR. Aqueous or particulate PAHs respectively show significant correlations with dissolved organic carbon, particulate organic matter, and chlorophyll a, suggesting that biological pumping effect regulates their distribution. The in situ partitioning coefficients (log K_oc) for PAHs are one order magnitude higher than the empirical log K_oc–log K_ow correlation. The bioconcentration factor (BCF) is slightly higher for the marine fish than for the freshwater fish. The above phenomena indicate that BCF may vary due to the diversity of fish species, feeding habits, and metabolism of PAHs in fish.     

Concentrations and transport of trace metals in the St. Lawrence River

Samples of raw water were collected in the St. Lawrence River during six sampling trips from August 1990 to April 1992. Water samples were analyzed for both dissolved and particulate phases for five trace metals. Partition coefficients (Kd) and metal fluxes were calculated in order to determine metal transport. A mass balance equation was used for the determination of the major metal sources to the St. Lawrence River and an estimation of metal loadings to the estuary was made. Average dissolved metal concentrations were found to be Cd 10 ng/L, Co 74 ng/L, Cu 64 ng/L, Fe 69 µg/L and Mn 700 ng/L. Particulate concentrations were (in µg/g) 1.68 for Cd, 31 for Co, 73 for Cu, 25 mg/g for Fe and 1.69 mg/g for Mn. Co, Fe and Mn were transported essentially in the particulate phase while Cd and Cu were predominantly found in the dissolved phase at 56% and 48% of the total metal concentration respectively. Log Kd values varied from 5.1 (for Cu) to 6.8 (for Mn). In the dissolved phase the major sources were found to be the Great Lakes and the Ottawa River whereas in the particulate phase Québec tributaries appear to be the most important. Industrial inputs are quite important in both the dissolved and the particulate phases for Cd, whereas other sources are very variable, especially for the dissolved phase.     

Air--sea gaseous exchange of PCB at the Venice lagoon (Italy)

Water bodies are important storage media for persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) and this function is increased in coastal regions because their inputs are higher than those to the open sea. The air-water interface is extensively involved with the global cycling of PCBs because it is the place where they accumulate due to depositional processes and where they may be emitted by gaseous exchange. In this work the parallel collection of air, microlayer and sub-superficial water samples was performed in July 2005 at a site in the Venice lagoon to evaluate the summer gaseous flux of PCBs. The total concentration of PCBs (sum of 118 congeners) in air varies from 87 to 273 pg m(-3), whereas in the operationally defined dissolved phase of microlayer and sub-superficial water samples it varies from 159 to 391 pg L(-1). No significant enrichment of dissolved PCB into the microlayer has been observed, although a preferential accumulation of most hydrophobic congeners occurs. Due to this behaviour, we believe that the modified two-layer model was the most suitable approach for the evaluation of the flux at the air-sea interface, because it takes into account the influence of the microlayer. From its application it appears that PCB volatilize from the lagoon waters with a net flux varying from 58 to 195 ng m(-2)d(-1) (uncertainty: +/-50-64%) due to the strong influence of wind speed. This flux is greater than those reported in the literature for the atmospheric deposition and rivers input and reveals that PCB are actively emitted from the Venice lagoon in summer months.     

Dynamic behaviour of polycyclic aromatic hydrocarbons in Brighton marina, UK

The distribution of polycyclic aromatic hydrocarbons (PAHs) between various phases is fundamental in the control of their movement and impact in the marine environment. In this study samples of water and sediments were regularly collected from Brighton marina, UK, to quantify the intensity, spatial and temporal variations of PAH contamination. The results show clearly that PAH behaviour in marine systems is highly complex, and controlled by the interplay of PAH sources, compound physicochemical properties, water and sediment movement, and field conditions. Levels of total PAHs (16 compounds) in the dissolved phase were found to vary between <2 and 11,400 ng/l, with higher values observed in the winter months. Total PAH concentration in sediment samples varied between 24 and 4710 ng/g dry weight. PAHs in water were dominated by low molecular mass compounds (2-ring), while PAHs in sediments were mainly derived from 2-4 ring compounds. In addition, dissolved concentrations were increased during sediment dredging and after a period of severe rainfall. PAHs in Brighton marina are likely to be from both pyrolytic and petrogenic sources; as a result, field-derived distribution coefficients for individual PAHs between sediment and water tend to follow the equilibrium partition models, although slight exceedance is apparent. The extended partition model incorporating soot carbon has achieved limited success in better predicting PAH behaviour.     

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.     

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.     

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%.