Supplemental Information 4: Raw data.

This study evaluated pollution levels in water and sediments of Península de Paraguaná and related these levels with benthic macrofauna along a coastal area where the largest Venezuelan oil refineries have operated over the past 60 years. For this, the concentration of heavy metals, of hydrocarbon compounds and the community structure of the macrobenthos were examined at 20 sites distributed along 40 km of coastline for six consecutive years, which included windy and calm seasons. The spatial variability of organic and inorganic compounds showed considerably high coastal pollution along the study area, across both years and seasons. The southern sites, closest to the refineries, had consistently higher concentrations of heavy metals and organic compounds in water and sediments when compared to those in the north. The benthic community was dominated by polychaetes at all sites, seasons and years, and their abundance and distribution were significantly correlated with physical and chemical characteristics of the sediments. Sites close to the oil refineries were consistently dominated by families known to tolerate xenobiotics, such as Capitellidae and Spionidae. The results from this study highlight the importance of continuing long-term environmental monitoring programs to assess the impact of effluent discharge and spill events from the oil refineries that operate in the western coast of Paraguaná, Venezuela

Assessment of coastal management options by means of multilayered ecosystem models

This paper presents a multilayered ecosystem modelling approach that combines the simulation of the biogeochemistry of a coastal ecosystem with the simulation of the main forcing functions, such as catchment loading and aquaculture activities. This approach was developed as a tool for sustainable management of coastal ecosystems. A key feature is to simulate management scenarios that account for changes in multiple uses and enable assessment of cumulative impacts of coastal activities. The model was applied to a coastal zone in China with large aquaculture production and multiple catchment uses, and where management efforts to improve water quality are under way. Development scenarios designed in conjunction with local managers and aquaculture producers include the reduction of fish cages and treatment of wastewater. Despite the reduction in nutrient loading simulated in three different scenarios, inorganic nutrient concentrations in the bay were predicted to exceed the thresholds for poor quality defined by Chinese seawater quality legislation. For all scenarios there is still a Moderate High to High nutrient loading from the catchment, so further reductions might be enacted, together with additional decreases in fish cage culture. The model predicts that overall, shellfish production decreases by 10%–28% using any of these development scenarios, principally because shellfish growth is being sustained by the substances to be reduced for improvement of water quality. The model outcomes indicate that this may be counteracted by zoning of shellfish aquaculture at the ecosystem level in order to optimize trade-offs between productivity and environmental effects. The present case study exemplifies the value of multilayered ecosystem modelling as a tool for Integrated Coastal Zone Management and for the adoption of ecosystem approaches for marine resource management. This modelling approach can be applied worldwide, and may be particularly useful for the application of coastal management regulation, for instance in the implementation of the European Marine Strategy Framework Directive

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.Postprint1,95

Development of an analytical method to detect metabolites of nitrofurans. Application to the study of furazolidone elimination in Vietnamese black tiger shrimp (Penaeus monodon)

Nitrofurans, banned antibiotics in European Union (EU), have often been found in imported aquaculture products in the past and are still found nowadays according to the Rapid Alert System for Feed and Food (RASFF) of the European Commission. A quantitative method based on liquid chromatography coupled to isotopic dilution tandem mass spectrometry (LC–IDMS/MS) was developed for the determination of the residues of four nitrofuran antibiotic residues in shrimps. The experimental protocol consisted of an acid-catalysed release of protein-bound metabolites, followed by derivatisation with 2-nitrobenzaldehyde (NBA). Then, a double liquid–liquid extraction with ethyl acetate was performed before LC–IDMS/MS analysis by positive electrospray ionisation (ES+) with multiple reaction monitoring (MRM) of two transitions per compound. An “in-house” validation of the method for shrimp analysis was conducted according to the EU criteria for the analysis of veterinary drug residues in foods. The decision limits (CCalpha) were 0.08–0.36 µg kg -1 and the detection capabilities (CCbeta) were 0.12–0.61 µg kg-1, which are both below the minimum required performance limit (MRPL) set at 1 µg kg -1 by the EU. The developed method was applied to evaluate the elimination of furazolidone residues in shrimp muscles after a contamination experiment. After 28 days of decontamination, a concentration of 115 µg kg-1 of furazolidone metabolite 3-amino-2-oxazolidinone (AOZ) was still measured in shrimp muscle