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.     

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.     

Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer

Polycyclic aromatic hydrocarbons (PAHs) were measured in the coastal sea surface microlayer (SML), the sub-surface waters (SSW) and the overlying atmosphere in order to investigate the influence of the SML on contaminant enrichment and air-sea exchange. Samples were collected at two contrasting locations of the NW Mediterranean, one urban influenced (off Barcelona, Spain) and another comparatively clean (off Banyuls-sur-Mer, France). Statistical data analysis confirmed the accumulation of PAHs in the SML with respect to the SSW (20.3+/-9.1 vs. 13.1+/-10.0 ng L(-1) in the dissolved phase; 709+/-207 vs. 158+/-111 ng g(-1) in the particulate phase). This accumulation was higher at the contaminated location (Barcelona station) compared with the more pristine one, with PAH enrichments 1.5 and 4.5 times higher for the dissolved and particulate phases, respectively, indicating that the enrichment of PAHs in the SML is dominated by particle transport processes.     

Environmental behavior of organotin compounds in the coastal environment of Xiamen, China

In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L(-1) dissolved in the water, 0.14-6.7 ng (Sn) L(-1) in suspended particulate matter and nd approximately 26 ng (Sn) g(-1) (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen's coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of (210)Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.     

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.     

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.     

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%.     

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.     

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.     

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.     

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.     

贵州省草海表层水体和沉积物间隙水中汞的含量和形态分布初步研究

运用金汞齐-冷原子荧光光谱法(CVAFS)和气相色谱技术(GC),对贵州省草海不同水文季节(枯水期和丰水期)表层水中汞的各种赋存形态,包括总汞(HgT)、溶解态汞(HgD)、活性汞(HgR)、颗粒态汞(HgP)、总甲基汞(MeHgT)、溶解态甲基汞(MeHgD)和颗粒态甲基汞(MeHgP)以及沉积物间隙水剖面中的溶解态总汞和甲基汞含量进行了测定.结果显示:草海表层水体总汞浓度为1.7-9.0ng/L,活性汞浓度为0.06-1.4ng/L,总甲基汞浓度为0.11-0.67ng/L.沉积物间隙水中溶解态汞浓度为8.6-39.6ng/L,溶解态甲基汞浓度为0.11-4.9ng/L.实验数据表明,草海湖水以溶解态汞为主,其占总汞的比例为枯水期87%,丰水期51%,溶解态汞与总汞呈显著相关(丰水期P<0.01;枯水期P<0.05),颗粒态汞与总汞也呈显著相关(丰水期P<0.01;枯水期P<0.05).溶解态甲基汞与总甲基汞呈显著相关(丰水期P<0.01;枯水期P<0.05),表明溶解态甲基汞控制总甲基汞的分布.沉积物间隙水溶解态汞与溶解态甲基汞浓度明显高于上覆水体,表明沉积物为草海湖水中汞的一个重要来源.     

Dissolved and particulate trace metals in a Scottish sea loch: an example of a pristine environment?

In the near pristine environment of a silled fjord on the west coast of Scotland samples were taken for the determination of dissolved and particulate trace metals (Fe, Mn, Cu, Ni, Cd, Zn and Pb), together with nutrient and hydrographic data, during 19 surveys carried out over a year. An indication of the pristine nature of the environment are the low concentrations of dissolved silicon, phosphate and nitrate which are considerably lower than those of coastal waters which are subject to larger anthropogenic burdens. Distributions of dissolved Cu, Ni and Cd were found to broadly reflect conservative mixing of freshwater and seawater with both end members having similar concentrations. The concentration of dissolved Cu and Ni in seawater entering upper Loch Linnhe (Cu 0.28 μg l⁻¹; Ni 0.26 μg l⁻¹) was consistent with the 1:1 conservative mix of Irish Sea water and North Atlantic surface water predicted from radio-caesium tracer experiments (Mackay & Baxter, 1985). Atmospheric input of trace metals to upper Loch Linnhe appeared to be a relatively minor term in the mass balance relative to fluvial inputs. Values of distribution coefficients Kd were similar to those previously reported for the coastal environment. Iron showed the strongest affinity for the suspended sediments; with particulate percentages of the total load usually greater than 80%. Lead and Mn showed a similar strong affinity to the particle phase. For Cu, Ni and Zn the mass of the element in the dissolved phase was generally greater than that in the particulate fraction. Cadmium, was least associated with the particles, with typically greater than 90% existing in the dissolved phase.     

Distribution and temporal variation of cadmium in the St. Lawrence river basin

Samples of raw water were collected at regular intevals at two transects in the St. Lawremce River and four of its tributaries from March to November 1991 and from April to June 1992. Water samples were analyzed for both the dissolved and the particulate phase for cadmium (Cd), organic carbon, iron and manganese. Mean dissolved Cd concentration was 10±5 ng/L and no spatial variability was observed. Higher concentrations were found during high flow periods, suggesting an uptake of cadmium by phytoplankton during summer. In addition, dissolved cadmium did not appear to be associated with either DOC, dissolved Fe or dissolved Mn. The mean particulate Cd concentration was 1.3±1.1 μg/g, with almost all stations presenting the same concentration except the Yamaska River, which had a concentration of 0.5±0.2 μg/g. Particulate Cd showed a negative correlation with suspended particulate matter and a positive correlation with particulate organic carbon and particulare manganese. Fifty-nine percent of the cadmium was found to be in the particulate phase. Partition coefficients for cadmium (Kd), organic carbon (Kc), iron (KdFe) and manganese (KdMn) were calculated for each sample. Log Kd varied from 3.9 to 5.9, with an average of 5.0±0.4. Log Kd decreased with increasing particulate, matter as did Log Kc and Log KdMn. No significant correlation was found between Log Kd and Log Kc, suggesting that the distribution of cadmium between the dissolved and the particulate phase is not influenced by the distribution of organic carbon. In contrast, positive correlations were observed between Log Kd, Log KdFe and Log KdMn. Cadmium distribution appears to be influenced by Fe and Mn distribution.     

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.     

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 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.     

多环芳烃在城市湖泊气-水界面上的交换

利用大流量采样器和半渗透膜装置对广州麓湖大气中气态多环芳烃和水体中溶解态多环芳烃进行了连续一年的观测,在此数据基础上,依据国内外通用的双膜理论计算了多环芳烃在广州麓湖水面上的交换通量.结果显示萘、苊、二氢苊的交换通量方向是由湖水挥发进入大气,其它主要化合物都是从大气进入水体;在单个化合物的交换通量中,以菲的通量值为最大,平均达13137.1ng/(m2·d),最高达到21211.22ng/(m2·d),其次为萘、荧蒽、蒽、芘、芴、二氢苊和苊等.各化合物交换通量的季节变化特点大部分都是在夏季达到最大值,在冬季交换通量降到最小值,但唯一例外的是芴,其交换通量却是在夏季降到最低值.     

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.