The influence of natural vs anthropogenic factors on trace metal(loid) levels in the Mussel Watch programme: Two decades of monitoring in the Spanish Mediterranean sea.

The spatial distribution and temporal trends of trace metals (i.e. Cd, Cu, Hg, Pb and Zn) and a metalloid (i.e. As) along the Spanish Mediterranean coast from 1993 to 2013 are presented with a new estimation of their background levels monitored using wild mussels. Over a 20 years period, yearly mussel monitoring was undertaken with a rigorous field sampling protocol using 3 pooled samples strategy (3 x n = 80, with 8 mussels in the 3.0 to 3.9 size categories at each site), obtained in the pre-spawning period (May-June) to minimize biological factors and seasonal variability, which is a fundamental element of the international programme. Spatial distribution was characterized every 5 years and temporal trends were determined in 11 locations. The main aims of the present long term study are to evaluate the environmental status of different coastal locations regarding trace metal levels and follow the evolution of these levels over time after the implementation of regulatory measures. Regarding spatial distribution, the highest values for Cd, Cu, Hg and Pb were found close to known highly anthopogenic cities or shipyard areas. However, As and Zn did not strictly follow this pattern, showing natural increased concentrations in the Levantine Balearic and Strait of Gibraltar-Alboran Sea demarcations respectively. These distributions are associated with the conjunction of two geological formation inputs (Massif Central in France and Iberian Pyritic Belt in Spain) and the oceanographic conditions in the adjacent coastal area. In the case of temporal trends, metal concentrations decreased significantly over time in most stations, confirming the effectiveness of the regulatory measures and prohibitions established under European legislation. Concentrations of Pb were above the established thresholds for human consumption in only 12-14% of the sampling areas. With the information obtained for this study, we estimate background concentrations and propose new Background Assesment Criteria (BAC) for the Spanish Mediterranean coast as a threshold criterion: 1.62 mg/kg d.w. for Cd, 8.75 mg/kg d.w. for Cu, 0.202 mg/kg d.w. for Hg and 2.83 mg/kg d.w. for Pb. Exceptions should exist for As and Zn, for which there should be different levels in each demarcation, due to the geological, hydrological and oceanographic peculiarities of the Spanish coast. For the Levantine-Balearic demarcation, the proposed background concentrations are 117 mg/kg d.w. for As and 200 mg/kg d.w. for Zn., whereas in the Strait of Gibraltar-Alboran Sea demarcation, they are 27.5 mg/kg d.w. for As, and 471 mg/kg d.w. for Zn. This work demonstrates the vital importance of defining the background levels of metal(loid)s at a regional or subregional level because, for areas not affected by anthropogenic causes which have high values as the result of natural processes, this would avoid the risk of constantly surpassing the levels proposed in directives.

Tracking temporal trend breaks of anthropogenic change in Mussel Watch (MW) databases.

The potential for structural changes in time trend concentrations of mercury (Hg), lead (Pb), cadmium (Cd), zinc (Zn), and copper (Cu) in the Mediterranean mussel, Mytilus galloprovincialis, was examined in Mussel Watch (MW) databases of metal pollution at eighteen coastal stations over a decadal period, from 1992 to 2007. Simultaneously, by using two statistical methods representing both the classical hypothesis-testing and the Bayesian approaches, we found single and multiple trend breaks for Hg (28% of the stations), Cd (17%), and Pb (11%) within trends in connection with anthropogenic and subtle natural environmental changes. Also called change point problems, if not accounted for, these could bias time trend investigations and interpretations. We calculated trend rate differences of 39% and switches up to 1 order of magnitude from classical linear trend assessments. We discuss sampling, analytical, and environmental (both natural and anthropogenic) sources of data set variabilities, showing that, in practice, the overall 16-year analytical performance could be as elevated as the yearly sampling reproducibility. We demonstrate that environmental time trend interpretations benefit from undertaking prior structural change analysis. After decades of MW marine chemical pollution assessments these have proven extremely useful, although the occurrence of trend breaks directly affects the long-term marine environmental monitoring strategies. Our results suggest a broader concept to design monitoring programs in agreement with rapid global anthropogenic and environmental changes.

A large scale survey of trace metal levels in coastal waters of the Western Mediterranean basin using caged mussels (Mytilus galloprovincialis).

A large scale study of trace metal contamination (Hg, Cd, Pb and Ni) by means of caged mussels Mytilus galloprovincialis was undertaken along the coastal waters of the Western Mediterranean Sea within the context of the MYTILOS project. Individual mussels from an homogeneous population (shell size 50 ± 5 mm) obtained from an aquaculture farm were consecutively caged and deployed at 123 sites located in the Alborán, North-Western, South-Western and Tyrrhenian sub-basins for 12 weeks (April-July) in 2004, 2005 and 2006. After cage recoveries, both the metal content in the whole mussel tissue and the allometric parameters were measured. Statistical analysis of the datasets showed significant differences in concentrations between sub-basins for some metals and mussel condition index (CI). Linear regression models coupled to the CI were revisited for the data adjustment of certain trace metals (Hg, Cd and Ni), and four level categories were statistically derived to facilitate interregional comparison. Seawater masses surrounding coastal areas impacted by run-off from land mineralised coasts and industrial activities displayed the highest concentration ranges (Hg: 0.15-0.31 mg kg(-1) dw; Cd: 1.97-2.11; Ni: 2.18-3.20 and Pb: 3.1-3.8), although the levels obtained in most of the sites fitted within moderate or low categories, and they could be considered as baseline concentrations. However, few sites considered little-influenced by human activities, at present, showed high concentrations of Cd, Ni and Pb, which constitute new areas of concern. Overall, the use of active biomonitoring (ABM) approach allowed to investigate trace metal contamination in order to support policy makers in establishing regional strategies (particularly, with regard to the European Marine Strategy Directive).

Contemporary 14C radiocarbon levels of oxygenated polybrominated diphenyl ethers (O-PBDEs) isolated in sponge-cyanobacteria associations.

Considerable debate surrounds the sources of oxygenated polybrominated diphenyl ethers (O-PBDEs) in wildlife as to whether they are naturally produced or result from anthropogenic industrial activities. Natural radiocarbon ((14)C) abundance has proven to be a powerful tool to address this problem as recently biosynthesized compounds contain contemporary (i.e. modern) amounts of atmospheric radiocarbon; whereas industrial chemicals, mostly produced from fossil fuels, contain no detectable (14)C. However, few compounds isolated from organisms have been analyzed for their radiocarbon content. To provide a baseline, we analyzed the (14)C content of four O-PBDEs. These compounds, 6-OH-BDE47, 2'-OH-BDE68, 2',6-diOH-BDE159, and a recently identified compound, 2'-MeO-6-OH-BDE120, were isolated from the tropical marine sponges Dysidea granulosa and Lendenfeldia dendyi. The modern radiocarbon content of their chemical structures (i.e. diphenyl ethers, C(12)H(22)O) indicates that they are naturally produced. This adds to a growing baseline on, at least, the sources of these unusual compounds.

Integrated assessment of oil pollution using biological monitoring and chemical fingerprinting.

A full assessment of the impact of oil and chemical spills at sea requires the identification of both the polluting chemicals and the biological effects they cause. Here, a combination of chemical fingerprinting of surface oils, tissue residue analysis, and biological effects measures was used to explore the relationship between spilled oil and biological impact following the grounding of the MSC Napoli container ship in Lyme Bay, England in January 2007. Initially, oil contamination remained restricted to a surface slick in the vicinity of the wreck, and there was no chemical evidence to link biological impairment of animals (the common limpet, Patella vulgata) on the shore adjacent to the oil spill. Secondary oil contamination associated with salvage activities in July 2007 was also assessed. Chemical analyses of aliphatic hydrocarbons and terpanes in shell swabs taken from limpet shells provided an unequivocal match with the fuel oil carried by the ship. Corresponding chemical analysis of limpet tissues revealed increased concentrations of polycyclic aromatic hydrocarbons (PAHs) dominated by phenanthrene and C1 to C3 phenanthrenes with smaller contributions from heavier molecular weight PAHs. Concurrent ecotoxicological tests indicated impairment of cellular viability (p < 0.001), reduced immune function (p < 0.001), and damage to DNA (Comet assay, p < 0.001) in these animals, whereas antioxidant defenses were elevated relative to un-oiled animals. These results illustrate the value of combining biological monitoring with chemical fingerprinting for the rapid identification of spilled oils and their sublethal impacts on biota in situ.

Critical evaluation of the determination of pharmaceuticals, personal care products, phenolic endocrine disrupters and faecal steroids by GC/MS and PTV-GC/MS in environmental waters.

An analytical method is described for the determination of a broad range of emerging and priority pollutants, together with sewage molecular markers in environmental waters. The step-by-step study of the GC/MS analyses focuses on the effects of experimental variables using a large volume injection (LVI) technique [a programmed temperature-vaporising (PTV) inlet], the evaluation of a clean-up step using classical and newer sorbents (i.e. Al-N, Fl, NH(2), PSA, Si, CN and DIOL), and the revision of how organic matter [i.e. humic acids (HA) content] affects method performance. Reproducibility and recoveries from spiked coastal water samples at different analyte concentrations (100, 250 and 500 ng L(-1)) as well as with different levels of spiked humic acids (2, 10 and 20 mg L(-1)) are reported indicating a good performance of the extraction procedure with low levels of HA (<10 mg L(-1)). The presence of HA is a critical parameter during the solid-phase extraction (SPE) procedures. Of the clean-up sorbents tested, CN and DIOL proved most efficient in cleaning-up the extracts with recoveries in the range of 66-77% and 100-114%, respectively for the selected analytes. Both GC/MS and PTV-GC/MS instrumental configurations were tested using final sewage effluents, riverine, estuarine and coastal water samples. However, limited applicability of the PTV inlet is reported for environmental applications, affording only a modest improvement in chromatographic signal-to-noise ratios.

Inputs and distributions of synthetic musk fragrances in an estuarine and coastal environment; a case study.

Synthetic musks are ubiquitous contaminants in the environment. Compartmental distributions (dissolved, suspended particle associated and sedimentary) of the compounds throughout an axial estuarine transect and in coastal waters are reported. High concentrations of Galaxolide (HHCB) and Tonalide (AHTN) (987-2098 ng/L and 55-159 ng/L, respectively) were encountered in final effluent samples from sewage treatment plants (STPs) discharging into the Tamar and Plym Estuaries (UK), with lower concentrations of Celestolide (ADBI) (4-13 ng/L), Phantolide (AHMI) (6-9 ng/L), musk xylene (MX) (4-7 ng/L) and musk ketone (MK) (18-30 ng/L). Rapid dilution from the outfalls is demonstrated with resulting concentrations of HHCB spanning from 5 to 30 ng/L and those for AHTN from 3 to 15 ng/L. The other musks were generally not detected in the estuarine and coastal waters. The suspended particulate matter (SPM) and sedimentary profiles and compositions (HHCB:AHTN ratios) generally reflect the distribution in the water column with highest concentrations adjacent to sewage outfalls.

Novel use of a whole cell E. coli bioreporter as a urinary exposure biomarker.

Bacterial bioreporters have substantial potential for contaminant assessment but their real world application is currently impaired by a lack of sensitivity. Here, we exploit the bioconcentration of chemicals in the urine of animals to facilitate pollutant detection. The shore crab Carcinus maenas was exposed to the organic contaminant 2-hydroxybiphenyl, and urine was screened using an Escherichia coli-based luciferase gene (luxAB) reporter assay specific to this compound. Bioassay measurements differentiated between the original contaminant and its metabolites, quantifying bioconcentration factors of up to one hundred-fold in crab urine. Our results reveal the substantial potential of using bacterial bioreporter assays in real-time monitoring of biological matricesto determine exposure histories, with wide ranging potential for the in situ measurement of xenobiotics in risk assessments and epidemiology.

Characterization of sea surface chemical contamination after shipping accidents.

A contamination survey was conducted after the beaching of the stricken cargo ship MSC Napoli in Lyme Bay on the south coast of Devon (UK). A grid of 22 coastal and offshore stations was sampled to investigate the extent of spilled oil and to screen for chemical contamination, as well as to evaluate the behavior of the oil at the air-sea interface. Samples were collected from the sea surface microlayer (SML) and from subsurface waters (SSW) at each station. The fuel oil spilled (IFO 380) was also analyzed. The determination of oil-related hydrocarbons (aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), terpanes, and steranes) and the screening for other harmful chemicals on the inventory of the MSC Napoli in the seawater samples, was performed by PTV-GC/ MS using large volume injection (LVI) techniques. Screening did not reveal the presence of any harmful chemicals other than petroleum-related compounds. Results afforded investigation of oil sources and spatial distributions of total PAH concentrations and enrichments in the sea surface microlayer (SML). Rather than a single source, oil fingerprinting analyses of the samples revealed a mixture of three types of oil: heavy fuel oil, lubricating oil, and a lighter oil (probably diesel oil). Enrichment factors (EF) in the SML (EF = C(SML)/C(SSW)) were calculated and, in the vicinity of the ship, approached 2000, declining with distance away from the wreck. These factors represent approximately a 1000-fold enrichment over typical coastal total PAH enrichments in the SML and reflected a clear petrogenic origin of the contamination (as demonstrated, for example, by a Fl/Pgamma ratio < 1). In addition, the spatial transport and fate (i.e., air-sea exchange processes and water column diffusion) of the oil-related hydrocarbons in the sea surface were investigated. Essentially, near the wreck, the SML was highly enriched in oil forming a visible sheen, both disrupting the normal air-seawater exchange processes and generating a downward diffusion flux of contaminants from the SML to the SSW. This was reflected by a higher occurrence of naphthalene relative to alkyl-naphthalenes in the SSW compared to the SML. The higher concentrations and different sources of oil found in the SML in comparison to those found in the SSW indicate that, if only subsurface water samples are investigated in isolation, the true extent and impact of a spill could be underestimated. It is important to simultaneously evaluate contamination in the sea surface during emergency response.

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.

Sources, distribution and behaviour of methyl tert-butyl ether (MTBE) in the Tamar Estuary, UK.

Negligible information is currently available concerning levels of the fuel additive methyl tert-butyl ether (MTBE) in European estuaries or coastal environments. MTBE was measured at selected potentially contaminated harbours and marinas, and throughout an axial transect of the Tamar Estuary, UK. Headspace solid-phase microextraction was used in combination with GC-MS for its determination. MTBE was detected in water samples from all stations at concentrations ranging from a few ng/l to a maximum of 194 ng/l (in a semi-enclosed harbour). Elevated levels were generally associated with motor vehicle and boating activities. The Tamar road and rail bridges provided a major input to the lower estuary, downstream of which conservative mixing appeared depressed, probably through volatilisation and possibly through salting-out. The selected analytical system (using a Carboxen/PDMS fiber) proved both rapid and highly sensitive (with a detection limit of 6 ng/l). During method development, salinity was shown to have a major influence in controlling the extraction efficiency and it was found necessary to adjust salinity in all samples (to 75% saturation) prior to extraction. From these tests, we (for the first time) estimated the Setschenow ("salting-out") constant of MTBE to be 0.11 l/mol.