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.     

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.     

A review of pollutants in the sea-surface microlayer (SML): a unique habitat for marine organisms

Boundary layers between different environmental compartments represent critical interfaces for biological, chemical and physical processes. The sea-surface microlayer (uppermost 1-1000 microm layer) forms the boundary layer interface between the atmosphere and ocean. Environmental processes are controlled by the SML, and it is known to play a key role in the global distribution of anthropogenic pollutants. Due to its unique chemical composition, the upper organic film of the SML represents both a sink and a source for a range of pollutants including chlorinated hydrocarbons, organotin compounds, petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and heavy metals. These pollutants can be enriched in the SML by up to 500 times relative to concentrations occurring in the underlying bulk water column. The SML is also a unique ecosystem, serving as an important habitat for fish eggs and larvae. Concentration ranges and enrichment factors of pollutants in the SML in different areas of the world's oceans have been critically reviewed, together with available toxicity data for marine biota found within the SML. Overall, the SML is highly contaminated in many urban and industrialized areas of the world, resulting in severe ecotoxicological impacts. Such impacts may lead to drastic effects on the marine food web and to fishery recruitment in coastal waters. Studies of the toxicity of fish eggs and larvae exposed to the SML contaminants have shown that the SML in polluted areas leads to significantly higher rates of mortality and abnormality of fish embryos and larvae.     

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.     

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.     

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.     

Dissolved/dispersed hydrocarbons,tarballs and the surface microlayer: Experiences from an IOC/UNEP Workshop in Bermuda,December, 1984

An intercomparison exercise was conducted at the Bermuda Biological Station for Research, Inc, Bermuda on 1–15 December 1984. It primarily involved the testing of the IOC Manual for monitoring oil and dissolved/dispersed petroleum hydrocarbons (DDPH) in marine waters and on beaches (IOC, Manuals and Guides, No. 13). An additional exercise sought to intercompare methodologies for the collection of sea surface microlayer samples.DDPH measurements in the inshore waters of Bermuda resulted in a mean concentration of 0.057 μg l⁻¹ of (n = 30) chrysene equivalents with a 60% relative standard deviation (RSD). Open ocean samples yielded a mean concentration of 0.011 μg l⁻¹ (n = 44) with a 65% RSD. These concentrations are extremely low and the results indicate that the method described in the Manual is sufficiently sensitive for the detection of ‘hot spots’The collection of beach tar using the method outlined in the Manual indicated that the data, when expresed as per metre of linear beach length, are an extremely good measure of oil contamination. The mean of 42 collections was 23.1 ± 14.4 g m⁻¹ in the first sampling period and the mean of 39 transects was 40.6 ± 17.7 g m⁻¹ on the second sampling period. Although 14 individuals took part in the sampling the results of individuals were consistent enough to demonstrate that beach tar collections are indeed valuable tools for monitoring contamination by petroleum in the marine environment.The operational manual for the sampling of the sea surface microlayer (IOC Manuals and Guides, No. 15), was also tested. The results indicated that this method collects reproduceable volumes of elevated concentrations of materials from the sea surface suitable at least for qualitative analyses. However, the spatial distribution and stability of surface films may render quantitative analyses less meaningful.     

The use of transplanted cultured tropical oysters (Saccostrea commercialis) to monitor Cd levels in North Queensland coastal waters (Australia)

Bivalves are commonly used to detect metal pollution in the marine environment. Commercially cultured Milky oysters (Saccostrea commercialis) were transplanted in various sites along the North Queensland coast and analyzed for two metals of potentially anthropogenic origin (Cd, Zn). To provide additional information, naturally occurring Black Lip oysters (Saccostrea echinata) were also collected at the transplantation sites. The study demonstrated that the oysters species transplanted are good bioindicators of these metal concentrations in tropical waters, sensitive to variations in the environment at concentrations which are much smaller than pollution signals commonly reported for temperate waters. Three transplant experiments were carried out from May 1999 to February 2000. Milky oysters transplanted to offshore areas (Orpheus Is., Kelso Reef) accumulated Cd in the soft parts whereas oysters sampled from cages placed in Ross Creek and the Herbert River estuaries showed a decrease in Cd concentration, which resulted from an increase in dry weight. Dry weight appeared to be an important covariant affecting Cd concentration in the oysters whereas it does not unambiguously affect Zn concentrations. For the duration of the experiments, oysters sampled from the Magnetic Is. reference site showed effectively constant Cd concentrations and total Cd contents which indicates that any seasonal cycle affecting metal concentration is weak. It was found that Cd accumulation in oysters increased as ambient dissolved Cd concentration decreased, from which it was concluded that for these oysters, the predominant source of Cd was from the particulate phase rather than the dissolved phase.     

Prevalence of microplastics in Singapore's coastal marine environment

Microplastics have been recently identified as marine pollutants of significant concern due to their persistence, ubiquity and potential to act as vectors for the transfer and exposure of persistent organic pollutants to marine organisms. This study documents, for the first time, the presence and abundance of microplastics (>1.6 microm) in Singapore's coastal environment. An optimized sampling protocol for the collection and analysis of microplastics was developed, and beach sediments and seawater (surface microlayer and subsurface layer) samples were collected from nine different locations around the coastline. Low density microplastics were separated from sediments by flotation and polymer types were identified using Fourier transform infrared (FTIR) spectrometry. Synthetic polymer microplastics identified in beach sediments included polyethylene, polypropylene, polystyrene, nylon, polyvinyl alcohol and acrylonitrile butadiene styrene. Microplastics were detected in samples from four out of seven beach environments, with the greatest quantity found in sediments from two popular beaches in the eastern part of Singapore. Polyethylene, polypropylene and polystyrene microplastics were also found in the surface microlayer (50-60 microm) and subsurface layer (1m) of coastal waters. The presence of microplastics in sediments and seawater is likely due to on-going waste disposal practices from industries and recreational activities, and discharge from shipping.     

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.     

Do UK coastal and estuarine water samples pose a phototoxic threat?

Many studies have investigated phototoxicity under controlled laboratory conditions, however, few have actually demonstrated it occurring in environmental samples. Here we report on the potential for UK marine coastal waters to demonstrate phototoxicity when tested using the oyster embryo (Crassostrea gigas) bioassay in the presence UV light. Subsurface water, sea surface microlayer samples and subsurface water samples that had been extracted through solid phase extraction (SPE) columns were analysed. Results demonstrated that the majority of samples failed to display any phototoxic potential. However, those collected from Belfast Lough did display an increase in toxicity when bioassays were performed in the presence of UV light when compared to identical samples assayed in the absence of UV light. Analysis of water samples at this location identified known phototoxic PAHs, pyrene and fluoranthene. These findings suggest the need to consider the potential UV light has when determining the toxicity of environmental samples.     

Evaluation of butyltin compounds in Maryland waters of Chesapeake Bay

A monthly sampling programme for dibutyltin (DBT), tributyltin (TBT) and tetrabutyltin (TTBT) was initiated for a period of one year (July 1985–June 1986) in the Maryland waters of Chesapeake Bay. Concentrations of the above butyltin species were evaluated in the microlayer and water column of eight sampling stations representing two small and two large marinas, a large harbour, two major river systems and a heavily used shipping channel. DBT concentrations in the microlayer were generally higher in the four marinas when compared with the other stations. The highest DBT concentration reported in the microlayer was 1156 ng l⁻¹. Mean microlayer TBT concentrations ranged from 54–310 ng l⁻¹ in the four marinas. Three TBT concentrations ranging from 1049–1171 ng l⁻¹ were reported in the microlayer of the marinas. TBT concentrations of 41 and 29 mg l⁻¹ were detected in the microlayer of a heavily used shipping channel (C & D Canal) during May and June. TTBT concentrations were not detected in the microlayer at most stations during the 12 month sampling period.Mean DBT concentrations in the water column ranged from 23–145 ng l⁻¹ in the four marinas. DBT concentrations in the water column of the other stations were < 35 ng l⁻¹. Mean water column concentrations of TBT ranged from 51–408 ng l⁻¹ in all four marinas. Peak concentrations of TBT were reported in May and June for the various marinas. The highest TBT concentration reported in the water column was 998 ng l⁻¹. TBT concentrations of 20–24 ng l⁻¹ were reported in one of the river systems (Potomac River). TTBT concentrations were not detected in the water column at most of the stations.     

Lead and copper in the waters of Raritan and Lower New York Bays

A survey of waters adjacent to this heavily urbanized and industrialized region showed concentrations of copper, 65 μg l.^?1 to be the highest reported to date for estuarine waters, and lead up to 13.9 μg l.^?1 Correlations between distributions of dissolved and total metal concentration in the water column, hydrography, and metal in the sediment were related to benthic studies in this area. Laboratory studies are cited which show the potential for adverse effects on marine animals at these metal concentrations.     

Intercomparison of soil pore water extraction methods for stable isotope analysis and interpretation of hillslope runoff sources

Intercomparison of soil pore water extraction methods for stable isotope analysis has been a focus of recent studies in relation to plant source waters, which found a wide isotopic variance depending on the extraction method. Few studies have yet explored extraction effects for mobile pore waters that relate to hillslope runoff. This is because it is extremely difficult in natural systems to control the boundary conditions in order to assess and compare impacts of pore water extraction on resulting hillslope flow. With our new semicontrolled experiments on outdoor mini‐hillslopes, we studied mixing and runoff processes by means of stable isotopes of water and quantified relations between pore water extraction methods. We tested the null hypothesis that nondestructive and destructive pore water sampling methods sample the same soil water pool. Three hillslopes were mounted on load cells, filled with loamy sand textured soils from the Landscape Evolution Observatoryat Biosphere 2, equipped with soil moisture and temperature sensors, a bottom outflow, and a surface runoff gauge for isotope sampling. We followed the precipitation isotopic composition over and through the soil profile. One hillslope was instrumented with suction cups, on the second we installed sampling ports for in‐situ soil water vapour measurements, and the third hillslope was sampled destructively for applying the centrifugation and vapour equilibrium methods. All hillslopes were sampled at four depths (0–10, 10–20, 20–30, and 30–40 cm) at three different downslope positions. ²H and ¹⁸O analyses were performed via laser spectroscopy. We found no isotopic differences between rainfall, surface runoff, and bottom outflow. The in situ vapour ports' soil isotope data showed the widest spread over all hillslope positions and depths. Centrifugation's and suction cups' isotope results plotted closest to the local meteoric water line and within the range of hillslope runoff and bottom outflow data. Hillslope position did not influence the soil isotope results. These results suggest caution be used in the field when selecting an extraction technique for matching soil waters to runoff waters. Soil suction lysimeters and centrifugation appeared to be the most appropriate tools in this regard.     

Distribution of dissolved free amino acids, dissolved inorganic nitrogen and chlorophyll a in the surface microlayer and subsurface water of the Yellow Sea, China

Concentrations of 14 different dissolved free amino acids (DFAA), dissolved inorganic nitrogen (DIN), and chlorophyll a were determined in the surface microlayer and subsurface waters at 41 stations in the Yellow Sea, China in April 2006. The concentrations of DFAA in the subsurface water ranged from 0.13 to 1.62 μM, with an average of 0.57±0.05 μM, while those in the surface microlayer varied between 0.22 and 2.6 μM, with an average of 0.94±0.08 μM. Major constituents of DFAA present in the study area were glycine, alanine, glutamic acid, serine and histidine. One-way analysis of variance (ANOVA) showed no significant difference in average mol fractions of DFAA between microlayer and subsurface water (F=0.0440, P=0.8355). Hierarchical cluster analysis of the station similarity based on the DFAA composition in both the surface microlayer and subsurface water separated three clusters of stations at the 70% Bray–Curtis similarity level. The average concentrations of chlorophyll a and DIN were 1.18 (0.34–4.44) μg L⁻¹ and 16.57 (3.98–49.59) μM in the subsurface water, and those in the surface microlayer were 1.30 (0.24–3.97) μg L⁻¹ and 18.56 (5.77–48.93) μM, respectively. Our results showed that concentrations of chlorophyll a (r²=0.7940, n=41, p<0.0001), DIN (r²=0.6939, n=41, p<0.0001) and DFAA (r²=0.2416, n=41, P=0.0011) in the microlayer were, respectively, correlated with their subsurface water concentrations, implying that there was a strong exchange effect between the microlayer and subsurface water. The enrichment factor of DFAA in the microlayer ranged from 0.47 to 2.24 with a mean of 1.88±0.16.     

Field validation, in Scotland and Iceland, of the artificial mussel for monitoring trace metals in temperate seas

The artificial mussel (AM), a novel chemical sampling device, has been developed for monitoring dissolved trace metals in marine environments. The AM consists of Chelex-100 suspended in artificial seawater within Perspex tubing and enclosed with semi-permeable polyacrylamide gel at both ends. To validate the field performance of the AM in temperate waters, we deployed AMs alongside transplanted blue mussels Mytilus edulis in coastal environments in Scotland (Holy Loch, Loch Fyne, Loch Striven and Millport) and Iceland (Reykjavikurh?fn, Gufunes, South of thornerney, Hofsvik, Hvalfj?rethur and Sandgerethi) for monitoring trace metals. While uptake patterns of Cd between the AM and M. edulis were highly comparable, discrepancies were found in the accumulation profiles of the other metals (Cu, Cr, Pb and Zn), in particular Zn. Nonetheless, the AMs gave a better resolution to accurately reveal the spatial difference in dissolved metal contamination when compared with M. edulis. AMs complement the use of mussels since AMs indicate dissolved metals in seawater, whereas uptake by mussels indicates a mixture of dissolved and particulate metals. Our results also indicated that historical metal exposure of the transplanted M. edulis could significantly confound their metal concentrations especially when the deployment period was short (i.e. <34d). This study suggested that the AM can overcome problems associated with variable biological attributes and pre-exposure history in the mussel, and provides a standardized and representative time-integrated estimate of dissolved metal concentrations in different marine environments.     

Plastic ‘scrubbers’ in hand cleansers: a further (and minor) source for marine pollution identified

Small, inconspicuous fragments of plastic, generally < 0.5 mm across (i.e. microlitter) derived from some hand cleaners and cosmetic preparations, and also used with some airblast cleaning media, are an unusual addition to post-consumer waste entering marine waters. The environmental significance of this material is unknown, but here is a further example of the intrusion of anthropogenic waste of dubious value into marine ecosystems. It could impact sea-surface microlayer ecosystems and the meiofauna of intertidal sediments. It is also speculated that these finely granulated plastics, once dispersed through the oceanic water column, could prejudice the results of some ambitious particulate carbon flux experiments as well as interfere with elemental and mineralogic composition analyses of suspended particles. They may also warrant attention when determining heavy metal concentrations in contaminated fine-grained sediments of estuarine and harbour environments.     

Trace metals in the northern North Sea

Cadmium, lead and copper have been determined in the dissolved and particulate phase for surface waters of the northern North Sea. Dissolved cadmium and copper show concentration gradients associated with salinity fronts which mark the boundary between coastal and ocean waters; lead does not. The particulate phase is shown to represent only a small fraction of the total metal concentration. Processes likely to be responsible for the observed distribution are discussed.