Comparative assessment of microplastics and microalgae as vectors of mercury and chlorpyrifos in the copepod Acartia tonsa.

Microplastics (MPs) raise concerns not only as pollutants themselves, but also due to their ability to act as vectors of pollutants adsorbed from seawater, transferring them to marine organisms. However, the relevance of MPs as carriers of pollutants compared to microalgae needs further exploration. This study compared the role of MPs (2-10 µm non-oxidized and 10-15 µm oxidized high-density polyethylene) and natural organic particles (Rhodomonas lens microalgae, MA) as carriers of mercury (Hg, 2.3 µg Hg/L) and chlorpyrifos (CPF, 1.0 µg CPF/L) to adult Acartia tonsa copepods, after 24-48 h exposure. Dose-response experiments were first performed with adult female copepods exposed to oxidized MPs (0.25-4.0 mg/L), waterborne Hg (0.01-10.0 µg/L) and Ox MPs + Hg (0.25-4.0 mg oxidized MPs/L + 0.50-8.0 µg Hg/L) for 48 h, to complement previous studies that focused on the pesticide CPF. Effects were evaluated with four replicates for physiological and reproductive responses (6 females/replicate), biochemical techniques (40 individuals/replicate) and Hg/CPF bioaccumulation measurements (1000 individuals/replicate). Copepods accumulated Hg/CPF similarly from dissolved pollutants (6204 ± 2265 ng Hg/g and 1251 ± 646 ng CPF/g) and loaded MPs (3125 ± 1389 ng Hg/g and 1156 ± 266 ng CPF/g), but significantly less from loaded MA (21 ± 8 ng Hg/g and 173 ± 80 ng CPF/g). After 24-48 h, copepods exposed to MPs + Hg/CPF showed generally greater biological effects than those exposed to dissolved Hg/CPF or to MA + Hg/CPF, although differences were not statistically significant. MA + CPF had significantly lower AChE inhibition (1073.4 nmol min-1 mg-1) and MA + Hg lower GRx induction (48.8 nmol min-1 mg-1) compared to MPs + Hg/CPF and dissolved Hg/CPF (182.8-236.4 nmol min-1 mg-1 of AChE and 74.1-101.7 nmol min-1 mg-1 of GRx). Principal component analysis suggested different modes of action for Hg and CPF.

Microplastics increase the toxicity of mercury, chlorpyrifos and fluoranthene to mussel and sea urchin embryos.

The objective of this study was to determine whether and to what extent microplastics (MPs) enhance the toxicity of pollutants as well as whether pollutant-loaded MPs act as relevant vectors of chemical pollutants. With this aim, the toxicity for mussel and sea urchin embryos of: 1) three dissolved pollutants (Pol): chlorpyrifos (CPF), fluoranthene (FLT) and mercury (Hg); 2) their mixture with Microplastics (MP + Pol); and 3) pollutant-loaded MPs (MPPol), was assessed. Analyses of CPF, FLT and Hg were also performed to evaluate the transfer among dissolved and particulate phases. In general, the 'MP + Pol' treatments were more toxic as 48-h EC50 (µg/L) than the 'Pol' treatments for sea urchin or mussel. The 48-h and 120-h EC50s (µg/L) for sea urchin showed little variation for CPF and MP + CPF, and no clear pattern was found for FLT and MP + FLT. The performed chemical analysis in the MPPol tests indicated that desorption was the main route to explain the observed toxicity of Hg and a relevant route for CPF and FLT. This study contributes to improve the knowledge about the interactions between MPs and chemical pollutants, which is fundamental for a more realistic ecological risk assessment in aquatic ecosystems.

Complications from the placement of a tension-free suburethral sling using the transobturator and retropubic methods for treatment of female urinary incontinence.

OBJECTIVE: The aim of our study was to retrospectively analyze surgical complications arising from the collocation of suburethral mesh in the lower urinary tract, using both the transobturator and retropubic methods. PATIENTS AND METHODS: During the period between November 2002 and June 2011, we retrospectively studied 190 patients that were treated for stress urinary incontinence using a tension-free suburethral sling. 50 patients were treated using the retropubic route (SPARC®), and 140 patients were treated using a transobturator (MONARC®). RESULTS: In total, 16.57% of the patients presented with intraoperative, immediate postoperative or later postoperative complications. We observed a higher rate of complications with patients who were operated on retropubically (26%) than with patients who were operated on using the transobturator method (12%). CONCLUSIONS: The rate of complications for our study was low, and was even lower in the case of transobturator tape. Thus, we usually used transobturator tape in the treatment of stress incontinence.

Comparative role of microplastics and microalgae as vectors for chlorpyrifos bioacumulation and related physiological and immune effects in mussels.

Microplastics (MP) are contaminants of concern per se, and also by their capacity to sorb dissolved chemicals from seawater, acting as vehicles for their transfer into marine organisms. Still, the role of MP as vehicles for contaminants and their associated toxicological effects have been poorly investigated. In this work we have compared the role of MP (high density polyethylene, HDPE, ≤22 µm) and of natural organic particles (microalgae, MA) as vehicle for chlorpyrifos (CPF), one of the most common pesticides found in river and coastal waters. We have compared the capacity of MP and MA to carry CPF. Then, the mussel Mytilus galloprovincialis has been exposed for 21 days to dissolved CPF, and to the same amount of CPF loaded onto MP and MA. The concentration of CPF in mussel' tissues and several physiological, energetics and immune parameters have been analyzed after 7 and 21 days of exposure. Results showed similar CPF accumulation in mussel exposed to MP and to MA spiked with CPF. This revealed that MP acted as vector for CPF in a similar way (or even to a lesser extent) than MA. After 21 days of exposure mussels exposed to MP spiked with CPF displayed similar or more pronounced biological effects than mussels exposed to dissolved CPF or to MA loaded with CPF. This suggested that the combined "particle" and "organic contaminant" effect produced an alteration on the biological responses greater than that produced by each stressor alone, although this was evident only after 3 weeks of exposure.

Linking biochemical and individual-level effects of chlorpyrifos, triphenyl phosphate, and bisphenol A on sea urchin (Paracentrotus lividus) larvae.

The effects of three relevant organic pollutants: chlorpyrifos (CPF), a widely used insecticide, triphenyl phosphate (TPHP), employed as flame retardant and as plastic additive, and bisphenol A (BPA), used primarily as plastic additive, on sea urchin (Paracentrotus lividus) larvae, were investigated. Experiments consisted of exposing sea urchin fertilized eggs throughout their development to the 4-arm pluteus larval stage. The antioxidant enzymes glutathione reductase (GR) and catalase (CAT), the phase II detoxification enzyme glutathione S-transferase (GST), and the neurotransmitter catabolism enzyme acetylcholinesterase (AChE) were assessed in combination with responses at the individual level (larval growth). CPF was the most toxic compound with 10 and 50% effective concentrations (EC10 and EC50) values of 60 and 279 µg/l (0.17 and 0.80 µM), followed by TPHP with EC10 and EC50 values of 224 and 1213 µg/l (0.68 and 3.7 µM), and by BPA with EC10 and EC50 values of 885 and 1549 µg/l (3.9 and 6.8 µM). The toxicity of the three compounds was attributed to oxidative stress, to the modulation of the AChE response, and/or to the reduction of the detoxification efficacy. Increasing trends in CAT activity were observed for BPA and, to a lower extent, for CPF. GR activity showed a bell-shaped response in larvae exposed to CPF, whereas BPA caused an increasing trend in GR. GST also displayed a bell-shaped response to CPF exposure and a decreasing trend was observed for TPHP. An inhibition pattern in AChE activity was observed at increasing BPA concentrations. A potential role of the GST in the metabolism of CPF was proposed, but not for TPHP or BPA, and a significant increase of AChE activity associated with oxidative stress was observed in TPHP-exposed larvae. Among the biochemical responses, the GR activity was found to be a reliable biomarker of exposure for sea urchin early-life stages, providing a first sign of damage. These results show that the integration of responses at the biochemical level with fitness-related responses (e.g., growth) may help to improve knowledge about the impact of toxic substances on marine ecosystems.

Mineral density and bone remodelling markers in patients with calcium lithiasis.

UNLABELLED: What's known on the subject? and What does the study add? Hypercalciuria is related with bone mineral density loss. This study demonstrates the relationship between recurrent calcium nephrolithiasis and bone mineral density loss and their correlation with bone markers. OBJECTIVES: • To show that a relationship exists between the loss of bone mineral density (BMD) and calcium renal lithiasis and that bone remodelling markers correlate with changes in BMD. • It is possible that many cases hypercalciuria are related to the increase of bone turnover and the predominance of bone resorption phenomena. PATIENTS AND METHODS: • The present study comprised a transversal investigation in three groups: group O, without lithiasis; group A, with a single episode of lithiasis; and group B, with relapsed calcium renal lithiasis. • An analysis was made of body mass index; abdominal X-ray and/or urography and renal ultrasonography; osteocalcin and ß-crosslaps bone markers; calcium and citrate concentrations in the urine; and femur and spinal column bone densitometry. • The results were analyzed by analysis of variance and Pearson's correlation coefficient. RESULTS: • Patients with relapsed calcium renal lithiasis present a greater BMD loss than those in the O or A groups. • Densitometry: T-score femur -0.2 group O, -0.5 group A, -1.2 group B (P= 0.001); T-score column -0.6 group O, -0.6 group A, -1.3 group B (P= 0.05). • A statistically significant negative correlation exists between values of ß-crosslaps and T-score femur (R=-0.251; P= 0.009) and T-score column (R=-0.324; P= 0.001); thus, a higher concentration of ß-crosslaps was accompanied by a lower value of the T-score and a greater loss of BMD. • A positive relationship is observed between ß-crosslaps and osteocalcin (R= 0.611; P < 0.001) and between calciuria and cocient ß-crosslaps/osteocalcin (R= 0.303; P= 0.001). CONCLUSIONS: • A statistically significant relationship is shown between the loss of BMD and relapsed calcium renal lithiasis. • Determination of bone remodelling markers (i.e. osteocalcin and ß-crosslaps) facilitates the diagnosis of osteopaenia/osteoporosis in these patients.

Sea snail (Hexaplex trunculus) and sea cucumber (Holothuria polii) as potential sentinel species for organic pollutants and trace metals in coastal ecosystems.

The seasonal bioaccumulation of trace metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs) in sea snail (Hexaplex trunculus) and sea cucumber (Holothuria polii) from Mar Menor lagoon were characterised. The highest concentrations of p,p'-DDE were detected in the central and south part of Mar Menor lagoon. However, the highest concentrations of metals in sea snail and holothurians were detected in the influence area of El Beal wadi. Biomagnification factors (BMF) in sea snail from cockle (sea snail-cockle concentration ratio) were higher than 5 for metal and organochlorinated compounds. However, similar concentrations were observed in both species for PAHs due to gastropods capability of metabolising these pollutants. Consequently, sea snail is proposed as a sentinel for trace metals, PCBs and OCPs in the coastal lagoons, not only due to its bioaccumulation and biomagnification capacity but also the easy sampling and amply distribution in many coastal areas.

Phthalates, organotin compounds and per-polyfluoroalkyl substances in semiconfined areas of the Spanish coast: Occurrence, sources and risk assessment.

In this work two sensitive areas of the Spanish coast located in the Atlantic (Ria de Vigo) and Mediterranean (Mar Menor lagoon) have been studied regarding their contamination by phthalates, organotin compounds and per-polyfluoroalkyl substances (seawater and sediments) in two different campaigns (spring and autumn in 2015). PFAS and OTCs were detected in seawater and sediments at low concentrations (few ng L-1 or ng g-1), whereas PAEs were detected at levels two orders of magnitude higher, particularly in Mar Menor lagoon due to its semi-confined characteristics. However, PAEs and OTCs concentration in sediments were higher in Ría de Vigo than in Mar Menor lagoon as a consequence of the influence of the important urban nuclei and port in that area. The ecological risk assessment revealed that in both areas tributyltin, dibutyltin and diethylphthalate pose a significant risk in sediments, whereas in seawater tributyltin in both areas resulted in a high risk.

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.

Multiresidue method for the determination of 32 human and veterinary pharmaceuticals in soil and sediment by pressurized-liquid extraction and LC-MS/MS.

An analytical chemical method has been developed for the simultaneous determination of 32 different pharmaceuticals in soils and sediments. The pharmaceuticals cover a varity of different compound groups. Soil samples were extracted with different solvents with the help of pressurized-liquid extraction (PLE) followed by clean-up using a solid-phase extraction (SPE) procedure. The purified extracts were analyzed by LC-MS/MS. The extraction method was evaluated by testing the following variables: extraction solvents, solvent pH, and temperature. Applying 20 g of soil/sediment and extracting with a mixture of methanol with aqueous ammonia solution (0.1 mol L(-1)) at 80 degrees C for 5 min in five cycles provided satisfactory recoveries between 66 and 114% with SD of between 1 and 14%. For preconcentration and purification tandem MAX-HLB cartridges were used. The volume and composition was optimized and the highest recoveries were obtained with a combination of methanol-aqueous ammonia solution. The limits of quantification (LOQs) were between 0.2 and 2 ng g(-1) and linearity higher than 0.98 for the majority of the selected pharmaceuticals. The method was successfully applied to soil samples collected from the Jerez de la Frontera agricultural region, irrigated with treated wastewater, and to sediment samples from the River Guadalete. The detection of nine pharmaceuticals including stimulants, antirheumatics, analgesics, anti-inflammatories, tranquilizers, and veterinary medicines at ng g(-1) concentration levels was achieved.

Identification of contaminants of emerging concern with potential environmental risk in Spanish continental shelf sediments.

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16-4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4-46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5-3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas. CAPSULE: Alkylphenols, phthalates and organotins may provoke adverse effects on Spanish coastal marine ecosystems from their sources to the sediment depositional areas.

PAHs, pesticides, personal care products and plastic additives in plastic debris from Spanish Mediterranean beaches.

In this study the role of plastic debris as a pollution vector has been evaluated by determining the concentrations of hydrophobic organic contaminants in polymers from three Western Mediterranean coastal areas as well as their potential transfer to seawater. Plastic debris was sampled at three Iberian Peninsula Southeastern beaches, each affected by different predominant anthropogenic activities (tourism, agriculture, urban activities, transport and industry). Plastic debris was characterized by attenuated total reflection Fourier-transform infrared spectrometry. The organic contaminants were extracted from plastics by ultrasonic extraction with methanol and quantified by stir bar sorptive extraction coupled to gas chromatography-mass spectrometry (GC-MS). In two areas, the desorption of these contaminants from plastic debris to seawater during 24 h was also evaluated. The contaminant groups considered in this study (polycyclic aromatic hydrocarbons (PAHs), personal care products (PCPs), current use pesticides (CUPs), organochlorinated compounds (OCPs, including polychlorinated biphenyls and organochlorinated pesticides) and plastic additives were found in polymers from the three areas. The most abundant contaminants were plastic additives and PCPs, underlining the relevance of the leaching of plastic components, and urban and tourism activities as typical pollution sources in the coastal areas. In general, large piece-to-piece variability was found for all polymers and areas mainly as a consequence of their different origin, exposition time, use and surface-to-volume ratio. This fact difficulted the visualization of significant differences between polymers or areas, but for CUPs, whose concentrations were significantly higher in Cape Cope than in the other areas due to the influence of close agricultural activities. PCPs and CUPs were desorbed partially in seawater for 24 h, particularly the most hydrophilic compounds such as triazines and other CUPs. However, a significant fraction of other contaminants (mainly PAHs) was retained, which suggests they can be transported far away from their origin.

Removal of natural organic matter and THM formation potential by ultra- and nanofiltration of surface water.

Natural organic matter (NOM) and trihalomethane formation potential (THMFP) removal were evaluated by ultrafiltration (UF) and nanofiltration (NF). Ten different raw water sources in Alicante province (SE Spain) were analysed. Five types of membranes of different materials were tested with a dead-end-type stirred UF cell. Additional measurements, such as dissolved organic carbon, ultraviolet absorbance (254nm), THMFP, ion concentration, pH, conductivity, etc. were made on raw water, permeates and concentrates. The SUVA value was used to determine the hydrophobicity of the water analysed. The elimination of NOM and THMFP is correlated with the molecular weight (MW) of NOM determined by size exclusion chromatography (SEC). The flux decline trends were correlated with cation concentration. NOM removal by UF is low, which correlates with the average MW determined by SEC with an average value of 922g/mol (between 833 and 1031g/mol). However, the NOM removal obtained with the NF90 and NF270 NF membranes for all water sources is almost complete (90%). THMFP removal is related to hydrophobicity and permeability of membrane. The NFT50 membrane removes almost 100% of the THMFP of more hydrophobic waters.

Ecotoxicological evaluation of the risk posed by bisphenol A, triclosan, and 4-nonylphenol in coastal waters using early life stages of marine organisms (Isochrysis galbana, Mytilus galloprovincialis, Paracentrotus lividus, and Acartia clausi).

This study assessed the environmental risk on coastal ecosystems posed by three phenolic compounds of special environmental and human health concern used in plastics and household products: bisphenol A (BPA), triclosan (TCS) and 4-nonylphenol (4-NP). These three chemicals are among the organic contaminants most frequently detected in wastewater. The most toxic compound tested was 4-NP, with 10% effective concentration at 11.1 µg L-1 for Isochrysis galbana, 110.5 µg L-1 for Mytilus galloprovincialis, 53.8 µg L-1 for Paracentrotus lividus, and 29.0 µg L-1 for Acartia clausi, followed by TCS (14.6 µg L-1 for I. galbana, 149.8 µg L-1 for M. galloprovincialis, 129.9 µg L-1 for P. lividus, and 64.8 µg L-1 for A. clausi). For all species tested, BPA was the less toxic chemical, with toxicity thresholds ranging between 400 and 1200 µg L-1 except for A. clausi nauplii (186 µg L-1). The relatively narrow range of variation in toxicity considering the broad physiological differences among the biological models used point at non-selective mechanisms of toxicity for these aromatic organics. Microalgae, the main primary producers in pelagic ecosystems, showed particularly high susceptibility to the chemicals tested. When the toxicity thresholds experimentally obtained were compared to the maximum environmental concentrations reported in coastal waters, the risk quotients obtained correspond to very low or low risk for BPA and TCS, and from low to high for 4-NP.

Potential transfer of organic pollutants from littoral plastics debris to the marine environment.

Plastic polymers act as passive samplers in air system and concentrate hydrophobic organic contaminants by sorption or specific interactions, which can be transported to other systems such as the marine environment. In this study plastic debris was sampled in the surrounding area of a Mediterranean lagoon in order to determine the concentration of persistent and emerging organic contaminants. More specifically, desorption of 91 regulated and emerging organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, current-use pesticides, personal care products, other pesticides and plastic additives) was characterized for the first 24 h from different polymers to seawater and the remaining content of these contaminants was also extracted by ultrasonic extraction with methanol. All samples were analyzed by Stir Bar Sorptive Extraction coupled to GC/MS. A significant fraction of sorbed contaminants in polymers was desorbed in the first 24 h, particularly for triazines and organophosphorus pesticides due to their lower hydrophobicity than other considered analytes. The remaining contaminants contained in plastics can be also transferred to seawater, sediments or biota. Considering 24 h desorbed fraction plus the remaining methanol extracted fraction, the highest transfer levels corresponded to personal care products, plastic additives, current-use pesticides and PAHs. This is the first study to show the relevance of the transport of organic contaminants on plastic debris from littoral areas to the marine environment.

Simultaneous determination of pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in seawater and interstitial marine water samples, using stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry.

A method for the simultaneous determination of semi-volatile organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine and organophosphorus pesticides) in marine samples has been developed, for the first time, using the stir bar sorptive extraction technique (SBSE) and thermal desorption coupled to capillary gas chromatography-mass spectrometry (SBSE-TD-GC-MS). Polydimethyl siloxane (PDMS) was used for the extraction of the selected analytes and two procedures have been optimised and validated, one for seawater samples (100 mL) and another for interstitial water samples (10 mL), using PDMS stir bars of 20 mm and 10 mm size, respectively. The extraction and analytical conditions, such as extraction time, matrix effects, sample volume and desorption time, were optimised. The proposed methods are sensitive, simple and show good linearity and detection limits lower than 1 ng L(-1) with seawater and lower than 10 ng L(-1) with interstitial marine water for the majority of compounds tested. Repeatability and reproducibility, expressed as relative standard deviation, have values lower than 20% for the majority of analytes considered. The recoveries for both sample volume procedures are higher than 60 and 70% for 10 and 100 mL, respectively, except for the more apolar (some PAHs and PCBs) and the more polar (some triazines) analytes which present lower values. The present SBSE/GC/MS method was applied for the analysis of trace organic contaminants in seawater and interstitial water samples from Cadiz Bay (SW of Spain). Terbutylazine, DDX and some PAHs were found at several seawater sampling points at ng L(-1) levels, and some PAHs in interstitial water too.

Levels and temporal trends of organochlorine contaminants in mussels from Spanish Mediterranean waters.

The levels and trends of organochlorine contaminants were determined along the Spanish Mediterranean coast from 2000 to 2013 using mussel, Mytilus galloprovincialis, as bioindicator species. The highest levels of PCBs and DDTs were found at industrial and urban locations, and at areas under the influence of the mouth of major rivers. Dieldrin and t-NNC were commonly detected, while HCHs, aldrin, isodrin, endrin and HCB were at levels not detectable at many areas. Significant declines on the levels of DDTs were observed at most of the areas studied. Conversely, no trends or weak downtrends for PCBs were observed in the areas more polluted by local sources, and in most areas less polluted, where PCBs inputs may be primarily from the atmosphere. Upward trends for PCBs were found in some areas from the Alborán Sea, probably related to the inputs of PCBs through the Strait of Gibraltar. Background concentrations for PCBs and p,p'-DDE have been calculated for this Mediterranean region.

Assessing environmental quality status by integrating chemical and biological effect data: The Cartagena coastal zone as a case.

Cartagena coastal zone (W Mediterranean) was chosen for a practical case study to investigate the suitability of an integrated indicator framework for marine monitoring and assessment of chemicals and their effects, which was developed by ICES and OSPAR. Red mullet (Mullus barbatus) and the Mediterranean mussel (Mytilus galloprovincialis) were selected as target species. Concentrations of contaminants in sediment and biota, and contaminant-related biomarkers were analysed. To assess environmental quality in the Cartagena coastal zone with respect to chemical pollution, data were assessed using available assessment criteria, and then integrated for different environmental matrices. A qualitative scoring method was used to rank the overall assessments into selected categories and to evaluate the confidence level of the final integrated assessment. The ICES/OSPAR integrated assessment framework, originally designed for the North Atlantic, was found to be applicable for Mediterranean species and environmental matrices. Further development of assessment criteria of chemical and biological parameters in sediments and target species from the Mediterranean will, however, be required before this framework can be fully applied for determining Good Environmental Status (GES) of the Marine Strategy Framework Directive in these regions.

Distribution of anionic and nonionic surfactants in a sewage-impacted Mediterranean coastal lagoon: inputs and seasonal variations.

In this work we have monitored the seasonal inputs, occurrence and distribution of the world's most widely used surfactants (linear alkylbenzene sulfonates, LAS, nonylphenol polyethoxylates, NPEOs, and alcohol polyethoxylates, AEOs) in Mar Menor lagoon (SE Spain) and its main tributary (El Albujón) for the first time. Concentration of target compounds was determined in both surface waters and sediments after solid phase extraction and pressurized liquid extraction, respectively, followed by liquid chromatography-mass spectrometry (LC-MS). There were significant differences in surfactant fluxes from El Albujón towards Mar Menor depending on the season and the day of the week, with maximum estimated annual inputs being detected for LAS (406 kg) and their metabolites, sulfophenyl carboxylic acids (482 kg). Average concentrations of surfactants in the lagoon were between 44 and 1665 µg/kg in sediment, and between 0.3 and 63 µg/L in water. These levels were significantly higher for samples collected near the shore than for those measured inside the lagoon itself. Overall, the occurrence and distribution of surfactants in the system could be explained due to a combination of different sources (surface and groundwater inputs, treated and untreated wastewater effluents, towns, ports, etc.) and simultaneous in-situ physicochemical and biological processes, with an special emphasis on degradation during warmer months.