Presence and distribution of current-use pesticides in surface marine sediments from a Mediterranean coastal lagoon (SE Spain).

The spatial and seasonal distributions of current-use pesticides (CUPs), including triazines, organophosphorus pesticides, and tributylphosphate, were characterized in surface sediments from the Mar Menor lagoon during 2009 and 2010. The impact of two flash flood events on the input of CUPs and their distribution in the lagoon were also assessed. The total (dissolved + sorbed phase) input of CUPs in the two flash floods through the El Albujón watercourse into the lagoon was estimated at 38.9 kg, of which 9.9 kg corresponded to organophosphorus pesticides and 5.5 kg to triazines. CUP distribution onto sediments was not homogeneous in the lagoon due to the different contaminant sources, sediment types, and the physicochemical and hydrodynamic conditions of the Mar Menor lagoon. Thirteen CUPs were detected in 2009 and 19 in 2010, including mainly herbicides, insecticides, and the additive tributylphosphate. Mean CUP concentrations in the lagoon were generally below 20 ng g-1, except for chlorpyrifos and tributylphosphate in 2010. The highest concentrations were detected in depositional areas of the lagoon, in the area of influence of the El Albujón watercourse and other wadis with groundwater contributions such as El Mirador (north) and Los Alcázares (east) and that of marine water from El Estacio channel. In fact, the maximum concentration was detected close to El Albujón watercourse (chlorpyrifos, 102.8 ng g-1 dry weight). Four herbicides, two insecticides, two fungicides, and tributylphosphate showed a risk quotient higher than 1, with that for chlorpyrifos ranging from 96 to 35,200 after flash flood events.

Impact of flash flood events on the distribution of organic pollutants in surface sediments from a Mediterranean coastal lagoon (Mar Menor, SE Spain).

The influence of flash flood events on the input and distribution of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorinated pesticides (OCPs) in surface sediments from the Mar Menor lagoon were characterized in this study. These contaminants were analyzed in surface water samples collected during two flash flood events in the main surface watercourse which flow into the Mar Menor lagoon. Surface sediments were sampled semiannually before and after flash flood events. The total input of PAHs, OCPs, and PCBs (sorbed + dissolved) during two flash flood events was estimated at 0.98, 1.32, and 0.34 kg, respectively, the main input corresponding to p,p'-DDE (1.00 kg). The distribution of organic contaminants in surface sediments was not homogeneous as a consequence of the presence of many simultaneous sources and different meteorological, hydrodynamic, and physicochemical conditions. As a consequence of flash flood events, p,p'-DDE concentrations in surface sediments increased significantly in the central and south zones of the lagoon. However, in the case of PCBs, a dilution effect was observed in the south zone after such events, reducing the environmental risk. These changes in the pollutant distribution persisted at least 1 year later (autumn 2010), showing that the impact of flood events in the distribution of persistent organic contaminants in Mediterranean coastal lagoons is of relevance according to the ecological risk assessment carried out. The impact of these events should be also considered in other coastal systems, especially in semiarid and semiconfined areas.

Occurrence and seasonal distribution of polycyclic aromatic hydrocarbons and legacy and current-use pesticides in air from a Mediterranean coastal lagoon (Mar Menor, SE Spain).

The occurrence and seasonal distribution of polycyclic aromatic hydrocarbons (PAHs) and legacy and current-use pesticides (CUPs) in air were characterized around the Mar Menor lagoon using both active and passive sampling devices. The seasonal distribution of these pollutants was determined at 6 points using passive samplers. Passive sampler sampling rates were estimated for all detected analytes using an active sampler, considering preferentially winter data, due to probable losses in active sampling during summer (high temperatures and solar irradiation). The presence of 28 compounds (14 CUPs, 11 PAHs and 3 organochlorinated pesticides) were detected in air by polyurethane passive sampling. The most commonly detected contaminants (>95% of samples) in air were chlorpyrifos, chlorpyrifos-methyl and phenanthrene. The maximum concentrations corresponded to phenanthrene (6000 pg m-3) and chlorpyrifos (4900 pg m-3). The distribution of contaminants was spatially and seasonally heterogeneous. The highest concentrations of PAHs were found close to the airport, while the highest concentrations of pesticides were found in the influence area of agricultural fields (western stations). PAH and herbicide concentrations were higher in winter than in the other seasons, although some insecticides such as chlorpyrifos were more abundant in autumn. The presence of PAHs and legacy and current-use pesticides in air confirmed their transference potential to marine coastal areas such as the Mar Menor lagoon.

Do pharmaceuticals bioaccumulate in marine molluscs and fish from a coastal lagoon?

The bioaccumulation of 20 pharmaceuticals in cockle (Cerastodema glaucum), noble pen shell (Pinna nobilis), sea snail (Murex trunculus), golden grey mullet (Liza aurata) and black goby (Gobius niger) was evaluated, considering their distribution throughout the Mar Menor lagoon and their variations in spring and autumn 2010. The analytical procedure was adapted for the different matrices as being sensitive and reproducible. Eighteen out of the 20 compounds analysed were found at low ngg(-1) in these species throughout the lagoon. Hydrochlorothiazide and carbamazepine were detected in all species considered. The bioaccumulation of pharmaceuticals was heterogeneous in the lagoon, with a higher number of pharmaceuticals being detected in fish (18) than in wild molluscs (8), particularly in golden grey mullet muscle (16). В-blockers and psychiatric drugs were preferentially bioccumulated in fish and hydrochlorothiazide was also confirmed in caged clams. The higher detection frequency and concentrations found in golden grey mullet suggested that mugilids could be used as an indicator of contamination by pharmaceuticals in coastal areas. To the best of our knowledge, this is the first study that shows data about hydrochlorothiazide, levamisole and codeine in wild marine biota.

Seasonal distribution of pharmaceuticals in marine water and sediment from a Mediterranean coastal lagoon (SE Spain).

The seasonal variations in the occurrence and distribution of pharmaceuticals were evaluated in seawater and sediment of Mar Menor lagoon from spring 2010 to winter 2011. A total of 20 pharmaceuticals in seawater and 14 in sediments were found at concentrations from low ngL(-)(1) up to 168ngL(-)(1) (azithromycin) in seawater and from low ngg(-1) up to 50.3ngg(-1) (xylazine) in sediments. Azithromycin, xylazine and metoprolol were the most ubiquitous compounds in seawater since they were found in all seawater samples collected. Seven compounds were quantified in both matrices: clarithromycin, erythromycin, hydrochlorothiazide, irbesartan, losartan, salicylic acid and valsartan. Seasonal distribution profiles revealed different sources of pollutants associated to both, El Albujón watercourse (which receives the input of a WWTP) and other non-controlled discharges, into the lagoon. In summer the highest concentrations in seawater for most of the pharmaceuticals were detected close to main touristic nuclei, probably as consequence of sources such as the excretion from bathers and/or other non-controlled discharges, these being significantly higher than in autumn and winter for antibiotics. On the contrary, the mean concentration of lorazepam was significantly higher in colder seasons than in warmer ones. Sulfamethoxazole, erythromycin and especially clarithromycin showed hazard quotients higher than 1 in seawater at some areas of this lagoon indicating a potential risk to aquatic organisms in such specific areas.

Input of pharmaceuticals through coastal surface watercourses into a Mediterranean lagoon (Mar Menor, SE Spain): sources and seasonal variations.

The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujón watercourse to the Mar Menor lagoon were determined by UPLC-MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, ß-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L(-1) for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow system, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujón watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).

Influence of an intensive agricultural drainage basin on the seasonal distribution of organic pollutants in seawater from a Mediterranean coastal lagoon (Mar Menor, SE Spain).

The seasonal distribution of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, organophosphorus pesticides, triazines and other organic pollutants in surface seawater from the Mar Menor lagoon (SE Spain) was characterized from spring 2009 to winter 2010 by stir bar sorptive extraction and thermal desorption followed by capillary gas chromatography coupled to mass spectrometry (SBSE-GC-MS). The most ubiquitous pollutants were chlorpyrifos, chlortal-dimethyl, terbuthylazine, naphthalene and propyzamide throughout the year. Insecticides and herbicides were predominant in summer and spring, and fungicides were more abundant in autumn and winter. Chlorpyrifos was predominant in autumn and spring; herbicides (propyzamide, terbuthylazine and terbuthylazine-desethyl) in autumn and fungicides (flutolanil, boscalid, cyprodinil) in autumn and winter. The highest concentrations for the majority of pollutants were detected in autumn as consequence of air and surface/ground water inputs, and above all of desorption from terrigenous materials deposited in sediments by two intense flash flood events (September 2009).

Seasonal input of regulated and emerging organic pollutants through surface watercourses to a Mediterranean coastal lagoon.

Seasonal input of organic pollutants through El Albujón Watercourse to the Mar Menor lagoon was estimated from Spring 2009 to Winter 2010, including regular periods and two flash flood events. 82 semivolatile organic pollutants (persistent organic pollutants, different groups of pesticides and others) were determined by stir bar sorptive extraction and thermal desorption followed by capillary gas chromatography coupled to mass spectrometry from surface waters with quantification limits of a few ngL(-1). Pesticide concentrations varied significantly along the watercourse due to the presence of different sources (groundwaters, wastewater effluent, tributary contributions, brackish waters, etc.) and physicochemical/biological processes that take place simultaneously. The most commonly detected analytes were propyzamide, triazine compounds and chlorpyrifos. A clear seasonal pattern has been detected, with a predominance of insecticides during Summer and of herbicides during Winter. The input of pesticides through this watercourse is particularly relevant during periods of heavy rain, representing more than 70% of total yearly input for many of them.