Sea Surface Microlayer Samples Research Articles

How do certain atmospheric aerosols affect Cu-binding organic ligands in the oligotrophic coastal sea surface microlayer?

It is still unclear how the chemical speciation of Cu in surface seawater is impacted by aerosols from various sources deposited on the sea surface, which is surprising, considering the environmental importance of Cu. Therefore, we used voltammetry to investigate Cu complexing capacity (CuCC) in the sea surface microlayer (SML) and in the underlying water (ULW) of the oligotrophic middle Adriatic Sea during February-July 2019. The focus was on the impacts of specific atmospheric processes such as open-fire biomass burning (BB), pollination season and Saharan dust intrusion. The presence of ligand class L2 (19.9-392.0, average 63.8, median 43.1) nM; log K2 (8.3-10.2, average 9.6, median 9.6) was observed in all samples, while ligand class L1 (40.5-76.1, average 53.6, median 48.9) nM; log K1 (10.3-11.1, average 10.6, median 10.5) was found in only 25% of SML samples. Throughout the period, the SML was enriched with organic ligands by a factor of up to 9.1 compared to the ULW, mainly due to the high sensitivity of the SML to specific atmospheric depositions. In addition, measurements with corresponding specific model aerosols were conducted to analyse their impacts on CuCC. Pollen directly affected CuCC in the SML by increasing the concentration of allochthonous ligands such as proteins. The deposition of BB aerosols rich in nutrients and trace metals stimulated the biological production of organic ligands, showing an indirect effect on CuCC delayed by up to two weeks. Finally, Saharan dust had a negligible impact on CuCC. This study illustrates the susceptibility of oligotrophic coastal area to the effects of pollen and open-fire BB aerosols in altering the Cu-binding organic ligands in the SML.

Mercury (Hg) in the "Skin" of the Ocean: Dissolved Gaseous Hg, Total Hg, and Hg Redox Chemistry in Sea Surface Microlayer and Implication for Air-Sea Hg Exchange.

The sea surface microlayer (SML) is the uppermost ∼1000 μm of the surface of the ocean. With distinct physicochemical properties and position relative to the adjacent subsurface waters (SSWs), the ubiquitous distribution and high dynamics of the SML greatly regulate the global air-sea gas exchange and biogeochemistry. Mercury (Hg) redox chemistry in surface seawaters and air-sea exchange of gaseous Hg (mainly Hg(0)) fundamentally control the global oceanic Hg cycle. However, the occurrence and transformation of Hg in the SML have been poorly quantified. Here we optimize the traditional SML sampling system to make it more suitable for dissolved gaseous Hg (DGM, mainly Hg(0)) sampling. We then assess the temporal and spatial variability of DGM, total Hg, dissolved organic carbon (DOC), and Hg redox chemistry in the SML and SSWs of diverse marine environments. Our data suggest a general DGM, total Hg, and DOC enrichment in the SML relative to the SSWs but with complex variability in time and space. The incubation experiments further reveal the complex characteristics of Hg redox chemistry between the SML and SSWs. We discuss important implications of the SML Hg cycle on air-sea Hg exchange and suggest wider investigations of the SML Hg cycle in the global hydrosphere.

Atmospheric deposition of biologically relevant trace metals in the eastern Adriatic coastal area

Aerosol (PM10), bulk deposition, sea surface microlayer (SML) and underlying water (ULW) samples were collected simultaneously during a field campaign at the middle Adriatic coastal site between February and July 2019, to assess the impact of atmospheric deposition (AD) of biologically relevant trace metals (TM) (Zn, Cu, Co, Ni, Cd and Pb) on the sea surface responses in an oligotrophic coastal region. Anthropogenic emissions from continental Europe, alongside local/regional domestic heating, likely affected the concentrations of Zn, Cd and Pb in aerosols during winter-early spring, while traffic emissions during the tourist season impacted Ni, Co and Cu aerosol concentrations. Additionally, open-fire biomass burning (BB) episodes caused considerable TM concentration increases, while Saharan dust intrusion in spring led to a 10-fold increase in Co concentrations in PM10 samples. These intensive episodes significantly affected the bulk deposition fluxes of TMs, showing that a small number of such extreme events, common to Mediterranean coastal areas, could be responsible for most of the AD. Enrichments and concentrations of total TMs in SML samples collected following BB events indicated that such events, along with high precipitation, influenced TM partitioning in surface water layers. We estimated that AD represents a significant source of TM to the shallow middle Adriatic coastal area, highlighting the need to further explore the atmosphere-sea surface links, to expand our understanding of the biogeochemistry of these important micronutrients and pollutants, including their impact on the aquatic community.

Floating particles with high copper concentration in the sea-surface microlayer.

This study sought to clarify whether suspended particles containing high Cu concentrations are present in the sea-surface microlayer (S-SML). For this reason, suspended particles (10-2000 μm) in the S-SML were collected periodically from a ship mooring pond during 2018-2020, and the acid-soluble Cu concentration in the suspended particles was measured as particulate Cu (P-Cu). The highest concentration of P-Cu in the S-SML of the pond was 75 μg L-1 with a 90th percentile value of 2.5 μg L-1. This is below P-Cu values reported for the S-SML in North American ports, but 140 times higher than this found in bulk seawater in the Atlantic Ocean. The highest P-Cu concentration in the S-SML of non-organism (abiotic) origin was 17 μg L-1, and the abiotic P-Cu to P-Cu ratio varied from 0.2 to 100%, likely depending on the quality and quantity of biogenic material in the S-SML samples. It is assumed that the S-SML particles examined here contain high Cu concentrations originating from ship antifouling paints.

Role of Sea Surface Microlayer Properties in Cloud Formation

To date, the relative contribution of primary marine organic matter to the subset of atmospheric particles that nucleate cloud droplets is highly uncertain. Here, cloud condensation nuclei (CCN) measurements were conducted on aerosolized sea surface microlayer (SML) samples collected from the North Atlantic Ocean during the NASA North Atlantic Aerosols and Marine Ecosystems Study (NAAMES), κ values were predicted for three representative high molecular weight (HMW) organic components of marine aerosol: 6-glucose, humic acid, and ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). The predicted κ values for pure organic aerosols varied by only ±0.01 across all of the organics chosen. For the desalted SML samples, calculations assuming an organic composition of entirely RuBisCO provided the closest predicted κ values for the desalted SML samples with a mean κ value of 0.53 ± 0.10. These results indicate that it is the sea salt in the SML which drives the cloud formation potential of marine aerosols. While the presence of organic material from the ocean surface waters may increase aerosol mass due to enrichment processes, cloud formation potential of mixed organic/salt primary marine aerosols will be slightly weakened or unchanged compared to sea spray aerosol.

The ice-nucleating activity of Arctic sea surface microlayer samples and marine algal cultures

Abstract. In recent years, sea spray as well as the biological material it contains has received increased attention as a source of ice-nucleating particles (INPs). Such INPs may play a role in remote marine regions, where other sources of INPs are scarce or absent. In the Arctic, these INPs can influence water–ice partitioning in low-level clouds and thereby the cloud lifetime, with consequences for the surface energy budget, sea ice formation and melt, and climate. Marine aerosol is of a diverse nature, so identifying sources of INPs is challenging. One fraction of marine bioaerosol (phytoplankton and their exudates) has been a particular focus of marine INP research. In our study we attempt to address three main questions. Firstly, we compare the ice-nucleating ability of two common phytoplankton species with Arctic seawater microlayer samples using the same instrumentation to see if these phytoplankton species produce ice-nucleating material with sufficient activity to account for the ice nucleation observed in Arctic microlayer samples. We present the first measurements of the ice-nucleating ability of two predominant phytoplankton species: Melosira arctica, a common Arctic diatom species, and Skeletonema marinoi, a ubiquitous diatom species across oceans worldwide. To determine the potential effect of nutrient conditions and characteristics of the algal culture, such as the amount of organic carbon associated with algal cells, on the ice nucleation activity, Skeletonema marinoi was grown under different nutrient regimes. From comparison of the ice nucleation data of the algal cultures to those obtained from a range of sea surface microlayer (SML) samples obtained during three different field expeditions to the Arctic (ACCACIA, NETCARE, and ASCOS), we found that they were not as ice active as the investigated microlayer samples, although these diatoms do produce ice-nucleating material. Secondly, to improve our understanding of local Arctic marine sources as atmospheric INPs we applied two aerosolization techniques to analyse the ice-nucleating ability of aerosolized microlayer and algal samples. The aerosols were generated either by direct nebulization of the undiluted bulk solutions or by the addition of the samples to a sea spray simulation chamber filled with artificial seawater. The latter method generates aerosol particles using a plunging jet to mimic the process of oceanic wave breaking. We observed that the aerosols produced using this approach can be ice active, indicating that the ice-nucleating material in seawater can indeed transfer to the aerosol phase. Thirdly, we attempted to measure ice nucleation activity across the entire temperature range relevant for mixed-phase clouds using a suite of ice nucleation measurement techniques – an expansion cloud chamber, a continuous-flow diffusion chamber, and a cold stage. In order to compare the measurements made using the different instruments, we have normalized the data in relation to the mass of salt present in the nascent sea spray aerosol. At temperatures above 248 K some of the SML samples were very effective at nucleating ice, but there was substantial variability between the different samples. In contrast, there was much less variability between samples below 248 K. We discuss our results in the context of aerosol–cloud interactions in the Arctic with a focus on furthering our understanding of which INP types may be important in the Arctic atmosphere.

Identification of tidal trapping of microplastics in a temperate salt marsh system using sea surface microlayer sampling

Microplastics are contaminants of increasing global environmental concern. Estuaries are a major transport pathway for land-derived plastics to the open ocean but are relatively understudied compared to coastal and open marine environments. The role of the “estuarine filter”, by which the supply of sediments and contaminants to the sea is moderated by processes including vegetative trapping and particle flocculation, remains poorly defined for microplastics land to sea transfer. Here, we focus on the sea surface microlayer (SML) as a vector for microplastics, and use SML sampling to assess microplastic trapping in a temperate marsh system in Southampton Water, UK. The SML is known to concentrate microplastics relative to the underlying water and is the first part of rising tidal waters to traverse intertidal and upper tidal surfaces. Sampling a salt marsh creek at high temporal resolution allowed assessment of microplastics in-wash and outflow from the salt marsh, and its relationship with tidal state and bulk suspended sediment concentrations (SSC), over spring and neap tides. A statistically significant decrease in microplastics abundance from the flood tide to the ebb tide was found, and a weak positive relationship with SSC observed.

Response of Phytoneuston Community to Organic Nitrogen and Phosphorus Revealed by HPLC-Pigments Method

The sea surface microlayer (SML) is the thin boundary layer between the ocean and the atmosphere. Phytoplankton community in the SML is known as phytoneuston and has a different community structure and biomass from the phytoplankton of the underlying bulk water. In this study, water samples were collected from the SML of Daya Bay in southern China in September, October, and December of 2013. Algal growth potential (AGP) tests were conducted by adding different forms of nitrogen (N), phosphorus (P) and silicate (Si). Phytoneuston grew well with both inorganic and organic nutrients, and showed comparable community structure after nutrient addition. A total of 16 pigments were analyzed in the SML samples collected from Daya Bay in this study. Phytopigments were dominated by the cyanobacteria-diagnostic pigment (zeaxanthin, Zea) in September and October, and by diatom-diagnostic pigment (fucoxanthin, Fuco) in December. The concentrations and proportions of Fuco increased greatly after the nutrient addition, and the concentrations and proportions of Zea decreased accordingly. Additionally, the diatom pigment index (DiatDP) increased after nutrient addition, and the prokaryotic pigment index (ProkDP) conversely decreased. The results suggested that massive occurrences of Zea and cyanobacteria are important characteristics of phytoneuston structure in Daya Bay especially in warm seasons, and nutrient addition especially Si addition promoted the growth of diatoms.

Seawater analysis by ambient mass-spectrometry-based seaomics

Abstract. An analytical method coupled to multivariate statistical analysis was developed based on transmission-mode direct analysis in real-time quadrupole time-of-flight mass spectrometry (TM-DART-QTOF-MS) to interrogate lipophilic compounds in seawater samples without the need for desalinization. An untargeted metabolomics approach is addressed here as seaomics and was successfully implemented to discriminate the sea surface microlayer (SML) from the underlying water (ULW) samples (n=22, 10 paired samples) collected during a field campaign at the Cabo Verde islands during September–October 2017. A panel of 11 ionic species detected in all samples allowed sample class discrimination by means of supervised multivariate statistical models. Tentative identification of the species enriched in the SML samples suggests that fatty alcohols, halogenated compounds, and oxygenated boron-containing organic compounds are available at the surface for air–water transfer processes. A subset of SML samples (n=5) were subjected to on-site experiments during the campaign by using a lab-to-field approach to test their secondary organic aerosol (SOA) formation potency. The results from these experiments and the analytical seaomics strategy provide a proof of a concept that can be used for an approach to identifying organic molecules involved in aerosol formation processes at the air–water interface.

Ammonia oxidizers in the sea-surface microlayer of a coastal marine inlet.

Planktonic archaea are thought to play an important role in ammonia oxidation in marine environments. Data on the distribution, abundance, and diversity of ammonia oxidizers in the coastal sea-surface microlayer (SML) are lacking, despite previous reports of high abundance of Thaumarchaeota in the SML of estuaries and freshwater lakes. Here, we failed to detect the presence of ammonia-oxidizing bacteria in any of our samples taken from a semi-enclosed marine inlet in Japan. Therefore, we shifted our focus to examine the archaeal community composition as well as the Thaumarchaeota marine group I (MG-I) and ammonia monooxygenase subunit A (amoA) gene copy numbers and composition in the SML and corresponding underlying water (UW, 20 cm). amoA gene copy numbers obtained by quantitative PCR were consistent with the typical values observed in the surface waters of oceanic and coastal environments where nitrification activity has been detected, but the copy numbers were two- to three-fold less than those reported from the surface layers and UW of high mountain lakes. Both amoA and MG-I 16S rRNA gene copy numbers were significantly negatively correlated with chlorophyll-a and transparent exopolymer particle concentrations in the SML. Communities of archaea and ammonia-oxidizing archaea in SML samples collected during low wind conditions (≤5 m s–1) differed the most from those in UW samples, whereas the communities in SML samples collected during high wind conditions were similar to the UW communities. In the SML, low ratios of amoA to MG-I 16S rRNA genes were observed, implying that most of the SML Thaumarchaeota lacked amoA. To our knowledge, our results provide the first comparison of ammonia-oxidizing communities in the coastal SML with those in the UW.

Blue pigmentation of neustonic copepods benefits exploitation of a prey-rich niche at the air-sea boundary

The sea-surface microlayer (SML) at the air-sea interface is a distinct, under-studied habitat compared to the subsurface and copepods, important components of ocean food webs, have developed key adaptations to exploit this niche. By using automated SML sampling, high-throughput sequencing and unmanned aerial vehicles, we report on the distribution and abundance of pontellid copepods in relation to the unique biophysicochemical signature of the SML. We found copepods in the SML even during high exposure to sun-derived ultraviolet radiation and their abundance was significantly correlated to increased algal biomass. We additionally investigated the significance of the pontellids’ blue pigmentation and found that the reflectance peak of the blue pigment matched the water-leaving spectral radiance of the ocean surface. This feature could reduce high visibility at the air-sea boundary and potentially provide camouflage of copepods from their predators.

Seasonal variations of the sea surface microlayer at the Boknis Eck Times Series Station (Baltic Sea).

The sea surface microlayer (SML) is the uppermost layer of the water column that links the ocean and atmosphere. It accumulates a variety of biogenic surface-active and buoyant substances, including gelatinous material, such as transparent exopolymer particles (TEP) and Coomassie stainable particles (CSP), potentially affecting air–sea exchange processes. Here, we studied the influence of the annual cycle of phytoplankton production on organic matter (OM) accumulation in the SML relative to the subsurface water (SSW). Sampling was performed monthly from April 2012 to November 2013 at the Boknis Eck Time Series Station (Baltic Sea). For SML sampling, we used the Garrett screen, while SSW samples were collected by Niskin bottles at 1 m depth. Samples were analyzed for carbohydrates, amino acids, TEP, CSP, chlorophyll a (SSW only) and bacterial abundance. Our data showed that the SML reflected the SSW during most parts of the year, with changes mainly responding to bloom formation and decay. OM composition during phytoplankton blooms clearly differed from periods of higher bacterial abundance. Of all components investigated, only the enrichment of total carbohydrates in the SML was inversely related to the wind speed indicating that wind-driven mixing also affected the accumulation of OM in the SML during our study.

Respiratory Microbiome of Endangered Southern Resident Killer Whales and Microbiota of Surrounding Sea Surface Microlayer in the Eastern North Pacific

In the Salish Sea, the endangered Southern Resident Killer Whale (SRKW) is a high trophic indicator of ecosystem health. Three major threats have been identified for this population: reduced prey availability, anthropogenic contaminants, and marine vessel disturbances. These perturbations can culminate in significant morbidity and mortality, usually associated with secondary infections that have a predilection to the respiratory system. To characterize the composition of the respiratory microbiota and identify recognized pathogens of SRKW, exhaled breath samples were collected between 2006–2009 and analyzed for bacteria, fungi and viruses using (1) culture-dependent, targeted PCR-based methodologies and (2) taxonomically broad, non-culture dependent PCR-based methodologies. Results were compared with sea surface microlayer (SML) samples to characterize the respective microbial constituents. An array of bacteria and fungi in breath and SML samples were identified, as well as microorganisms that exhibited resistance to multiple antimicrobial agents. The SML microbes and respiratory microbiota carry a pathogenic risk which we propose as an additional, fourth putative stressor (pathogens), which may adversely impact the endangered SRKW population.

Diversity of yeasts associated with the sea surface microlayer and underlying water along the northern coast of Taiwan

Yeast communities inhabiting the sea surface microlayer (SSML) on the northern coast of Taiwan were examined using a cultivation method and compared with those inhabiting the underlying water (UW) at a 50-cm depth. Culturable yeasts were recovered from the SSML and UW samples collected in the morning during 4 field campaigns, and 420 strains were isolated. The 420 isolates were grouped into 43 species using a polyphasic molecular approach, including sequence analysis of the 26S rDNA D1/D2 domain and 5.8S-ITS region. From the SSML samples, 12 genera and 39 species, including 7 new species of Cryptococcus sp. (1), Candida spp. (4), and Rhodotorula spp. (2), were isolated. From the UW samples, 10 genera and 21 species, including one new species of Rhodotorula sp. (1), were isolated. Rhodotorula mucilaginosa was the most abundant species present in the yeast community in SSML (37.6%) and UW (21.6%) samples. Basidiomycetous yeasts (63.6%) and pigmented yeasts (64.5%) comprised the major yeast population. The yeast community in the SSML had a higher species number and abundance than the UW. Moreover, although the majority of yeast community species were from the SSML, individual species distribution in the SSML was unequal.

Large accumulation of micro-sized synthetic polymer particles in the sea surface microlayer.

Determining the exact abundance of microplastics on the sea surface can be susceptible to the sampling method used. The sea surface microlayer (SML) can accumulate light plastic particles, but this has not yet been sampled. The abundance of microplastics in the SML was evaluated off the southern coast of Korea. The SML sampling method was then compared to bulk surface water filtering, a hand net (50 μm mesh), and a Manta trawl net (330 μm mesh). The mean abundances were in the order of SML water > hand net > bulk water > Manta trawl net. Fourier transform infrared spectroscopy (FTIR) identified that alkyds and poly(acrylate/styrene) accounted for 81 and 11%, respectively, of the total polymer content of the SML samples. These polymers originated from paints and the fiber-reinforced plastic (FRP) matrix used on ships. Synthetic polymers from ship coatings should be considered to be a source of microplastics. Selecting a suitable sampling method is crucial for evaluating microplastic pollution.

Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air–water interface and of the sea surface microlayer

Abstract. Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acids (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air–seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) University of Colorado light-emitting diode cavity-enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas-phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon–carbon double bonds in the PUFA molecules. In addition, two highly reactive dicarbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and < 1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples.

A comparative study of phytoneuston and the phytoplankton community structure in Daya Bay, South China Sea

Environmental parameters and phytoplankton communities in the sea surface microlayer (SML), subsurface water (SSW) and sub-bottom water (SBW) were surveyed in Daya Bay, South China Sea, from May 2007 to April 2008. A total of 142 taxa were identified, including 88 diatoms and 32 dinoflagellates. Diatoms represented 88.6%, 91.5% and 48.4% of total phytoplankton abundance in the SML, SSW and SBW, respectively. The phytoneuston community differed markedly from the phytoplankton due to a major increase in the proportion of cyanobacteria, comprising 42.1% of the total phytoneuston based on the microscopic observation. Cyanobacteria were highly enriched in the SML, with an average enrichment factor (EF) of 4.42 and an enrichment frequency of 100%. Diatoms, dinoflagellates, overall phytoplankton and chlorophyll a were depleted in the SML samples, yet there might be some small sized phytoneuston especially those of flagellates that were not accurately measured under the microscopic examination. All nutrients were enriched in the SML, especially phosphorus. In contrast with the negative correlations found between nutrients and total phytoplankton, the cyanobacteria showed significantly positive relationships with nutrients and negative relationships with total phytoplankton and diatoms. The results of the study suggest that the phytoneuston in Daya Bay is a unique community jointly dominated by cyanobacteria and diatoms. In contrast, diatoms alone dominate the phytoplankton community in the bulk water. These changes in the phytoneuston community may be indicators of the particular environmental changes in Daya Bay, such as increasing water temperature, global warming, high nutrient loads and increased dissolved organic nutrients.

Technical Note: Comparison of storage strategies of sea surface microlayer samples

Abstract. The sea surface microlayer (SML) is an important biogeochemical system whose physico-chemical analysis often necessitates some degree of sample storage. However, many SML components degrade with time so the development of optimal storage protocols is paramount. We here briefly review some commonly used treatment and storage protocols. Using freshwater and saline SML samples from a river estuary, we investigated temporal changes in surfactant activity (SA) and the absorbance and fluorescence of chromophoric dissolved organic matter (CDOM) over four weeks, following selected sample treatment and storage protocols. Some variability in the effectiveness of individual protocols most likely reflects sample provenance. None of the various protocols examined performed any better than dark storage at 4 °C without pre-treatment. We therefore recommend storing samples refrigerated in the dark.

Distributions of dissolved monosaccharides and polysaccharides in the surface microlayer and surface water of the Jiaozhou Bay and its adjacent area

Sea surface microlayer (SML) samples and corresponding bulk surface water (SW) samples were collected in the Jiaozhou Bay and its adjacent area in July and November 2008. The average concentrations of dissolved monosaccharides (MCHO) and polysaccharides (PCHO) revealed similar temporal variability, with higher concentrations during the green-tide period (in July) than during the non-green-tide period (in November). Average enrichment factors (EF) of MCHO and PCHO, defined as the ratio of the concentration in the SML to that in the SW, were 1.3 and 1.4 in July, respectively, while those values in November were 1.9 and 1.6. Our data also showed that the concentrations of MCHO and PCHO in the SML were strongly correlated with those in the SW, indicating that most of the organic materials in the SML came from the SW. The total dissolved carbohydrate concentrations (TDCHO) in the bulk surface water were closely correlated with salinity during the cruises (July: r=−0.580, n=18, P=0.01; November: r=−0.679, n=26, P<0.001), suggesting that riverine input had an important effect on the distribution of TDCHO in surface seawater of the study area.

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.