Greenhouse gas assemblages (CO2, CH4 and N2O) in the continental shelf of the Gulf of Cadiz (SW Iberian Peninsula).

This study examines the simultaneous water-atmosphere exchange of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) on the continental shelf of the Gulf of Cadiz, as well as the effect it has in terms of the radiative balance in the atmosphere, between 2014 and 2016. The experimental database consists of new measurements of the spatial and seasonal distribution of CO2 partial pressure (pCO2) and N2O concentration in 2016. pCO2 shows a wide range of variation influenced mainly by seasonal thermal variations (8.0 µatm 0C-1), as well as with the relative intensity of biological activity. There is experimental evidence of a progressive increase of pCO2 over the last 2 decades, with an estimated gradient of 4.2 ± 0.7 µatm y-1. During 2016, the Gulf of Cadiz acted as a slight source of CO2 to the atmosphere, with a mean flux of 0.4 ± 2.2 mmol m-2 d-1. The analysis of concentration variations in the water column shows that nitrification is the main N2O production process in the study area, although in the more coastal zone there are signs of inputs related to continental and sediment contributions, most probably induced by denitrification processes. In 2016, the Gulf of Cadiz acted as a weak sink of atmospheric N2O, with a mean flux of -0.1 ± 0.9 µmol m-2 d-1. From previous studies, performed with a similar methodology, an interannual database (2014-2016) of water-atmosphere fluxes of CO2, CH4 and N2O, normalized to the mean wind speed in the area, has been generated. Considering their respective Global Warming Potential (GWP) a joint greenhouse gasses (GHG) flux, expressed in CO2 equivalents of 0.6 ± 2.0 mmol m-2 d-1, has been estimated, which extended to the area of study indicates an approximate emission of 67.9 Gg CO2 y-1. However, although there is a high uncertainty associated with the spatial, temporal and interannual variations of CO2, CH4 and N2O fluxes in the Gulf of Cadiz, the exchange of greenhouse gasses could be influencing a radiative forcing increase in the atmosphere. When considering the available information on local and global estimates, the uncertainty about the effect of the joint exchange of GHGs to the atmosphere from the coastal seas increases significantly.

Dissolved organic matter distribution in the water column and sediment pore water in a highly anthropized coastal lagoon (Mar Menor, Spain): Characteristics, sources, and benthic fluxes.

Coastal lagoons are among the most productive and biodiverse systems in the world and are important sentinels of climate change. The Mar Menor is one of the largest coastal lagoons in the Mediterranean, providing a variety of ecosystem services and resources to the community. However, in recent decades this lagoon has suffered drastic changes and degradation caused by human activities. We analyzed the concentration of dissolved organic carbon (DOC) and the optical properties of dissolved organic matter (DOM) in the water column and sediment pore water during the summer and winter of 2018 and during eighteen months from 2016 to 2018. Overall, we found that the composition of DOM is mainly related to and enhanced by anthropogenic activities and microbial metabolism. DOM enters the lagoon via urban and agricultural runoff, drainage systems, and wastewater treatment plants. Additionally, strong microbial metabolism in sediments leads to differences in DOM composition between water and sediments. In the water column, humic-like components accounted for 71 % of the total DOM, while protein-like compounds were most abundant in sediment pore water. We observed a strong seasonal variability associated with precipitation and the system collapse in 2016 (phytoplankton bloom), which resulted in the death of 80 % of macrophytes. The sediments act as a source of DOM to the overlying water, likely due to relatively high organic matter content and intense microbial activity, primarily through anaerobic pathways. Benthic fluxes of DOC ranged from 5.24 to 33.30 mmol m-2 d-1, being higher in winter than summer 2018 and decreasing from north to south, likely related to lower residence time in the northern basin, groundwater discharge and accumulation of organic matter from the dead meadows. We estimate a net flux of DOC from the Mar Menor toward the Mediterranean Sea of 1.57 × 107 mol yr-1.

Dynamic of CO2, CH4 and N2O in the Guadalquivir estuary.

The concentration of dissolved CH4 and N2O, as well as the partial pressure of CO2 (pCO2) were studied in the Guadalquivir estuary. Samples were taken in March and April 2018 and 2019, under different rainy and tidal conditions. The available database for summer 2017 (Sierra et al., 2020) was included in the interpretation of the factors that determine the variability of these gases in the Guadalquivir estuary. Two different types of samplings were carried out: a longitudinal transect across the river with salinity values close to zero and another one during two consecutive tidal cycles in the mouth of the estuary. The highest concentrations were found in the upper zone of the estuary and during the low tide. This distribution was related to 4 factors: temperature, salinity, exchange with the atmosphere, and biochemical processes together with the river inputs. Temperature is one of the factors that clearly seems to determine the distribution of gases and fluxes, showing the highest values in the upper zone during the summer of 2017. Intense rains cause a dilution effect of the gas in the water column, this provoked, during the season of spring 2018, an increase in the salinity factor in the distribution of gases in the middle zone. High concentrations of the gases have been linked to production processes in the water column, as well as to benthic production and lateral inputs. While the gases concentrations at the mouth presented values close to those of the equilibrium with the atmosphere, the fluxes in the upper zone of the estuary reached average values of 89.6 mmol m-2 d-1, 121.7 µmol m-2 d-1 and 59.9 µmol m-2 d-1 for CO2, CH4 and N2O, respectively. Generally, water-atmosphere fluxes are positive through the whole study, which means that the estuary acts as a source of these gasses to the atmosphere.

Linkages between greenhouse gases (CO2, CH4, and N2O) and dissolved organic matter composition in a shallow estuary.

Estuarine systems receive large amounts of organic matter that enhance the production of greenhouse gases (GHGs), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Despite considerable research on GHGs and dissolved organic matter (DOM) distribution in estuaries, little is known about the linkage between these gases and DOM composition. Here we evaluated the relationship between three GHGs (CO2, CH4, and N2O) and DOM composition, determined through optical properties, in Guadalete estuary (Bay of Cadiz, Spain). The partial pressure of CO2, and CH4 and N2O concentrations ranged between 332.8 and 6807.1 µatm, 19.9-6440.1 nM, and 6.8-283.9 nM, respectively. Thus, the Guadalete estuary was a source of CO2, CH4 and N2O to the atmosphere. We validated three PARAFAC components related to humic-like fluorescence from terrestrial, microbial and effluent sources, and one with protein-like material. Humic-like components accounted for 86% ± 6% of the total FDOM pool, indicating a predominantly allochthonous DOM origin. The three GHGs were significantly linked to DOC concentration and DOM composition, exhibiting different patterns in these linkages. Terrestrial and microbial humic-like substances with increasing aromaticity might enhance pCO2 in Guadalete estuary. Dissolved CH4 concentrations showed the strongest relationship with DOM composition, indicating that humic and protein-like material are linked with their distribution. In contrast, dissolved N2O was only related with the protein-like fraction and with humic-like material derived from anthropogenic activities (sewage and agriculture). Our results further indicate that a possible coupling between benthic fluxes of GHGs and DOM might be occurring in this shallow estuary. We conclude that it is important to account for DOM composition when studying GHGs distribution in estuarine systems to understand their roles and potential responses associated with climate change.

"Greenhouse gas dynamics in a coastal lagoon during the recovery of the macrophyte meadow (Mar Menor, SE Spain)".

The Mar Menor is a hypersaline coastal lagoon with salinity values ranging from 41.9 to 45.5. The system is subjected to a high anthropic pressure that causes an intense eutrophication process, followed by a recovery of the macrophyte meadows. This study focuses on the distribution of the main greenhouse gases (CO2, CH4 and N2O) and was carried out in the extreme seasonal conditions of winter and summer during the year 2018. Sediment-water-atmosphere exchanges and biochemical processes in the water column appeared to be the main factors to explain the variability of these gases. Dissolved Inorganic Carbon (DIC), CH4 and N2O benthic fluxes values obtained in this study, were of 91 ± 29 mmol m-2 d-1, 3.9 ± 1.9 µmol m-2 d-1 and -0.65 µmol m-2 d-1, respectively, along with an important seasonal variation observed, with an increase of DIC and CH4 benthic fluxes during the summer season. Mean values of partial pressure of CO2 (pCO2) in surface water were of 579 µatm in winter and 464 µatm in summer, therefore we can establish that the Mar Menor acts as a source of this gas emitting 3.3 ± 3.0 mmol CO2 m-2 d-1 to the atmosphere. In spite of this, the Mar Menor has a strong autotrophic behaviour partly due to the recovery of the macrophyte meadows, presenting an estimated NEP of 101 mmol m-2 d-1. Regarding to CH4, the mean fluxes to the atmosphere were of 8.0 ± 5.8 µmol m-2 d-1 and there was evidence of CH4 production in the water column that increased in summer. Last of all, in the case of N2O the system acts as a sink with values of -0.65 ± 0.5 µmol m-2 d-1, presenting an intake of N2O that is usually detected in pristine systems.

Sources and coastal distribution of dissolved organic matter in the Gulf of Cadiz.

Dissolved organic matter (DOM) is a major component of the organic matter pool, playing a key role in the global ocean functioning. However, studies on DOM in waters of many ocean regions, such as the Gulf of Cadiz (GoC), are poorly known. Advanced aquatic sensors enable autonomous for long-term deployments in situ collection of high frequency DOM data using fluorescent dissolved organic matter (FDOM) as a proxy. The present study evaluates the relevance of FDOM, the estuarine influence and the environmental factors that determine its spatial distribution in the GoC. Our results suggest that the GoC water mass, under the estuarine influence of three main rivers, is receiving large amounts of DOM transported mainly by Guadalquivir and Guadiana rivers and much less from Tinto-Odiel. Salinity is the main factor explaining the FDOM variability within the Guadalquivir and Guadiana rivers and in the inner shelf of the GoC. In the outer shelf of the GoC, plankton-produced DOM could explain the persistent spatial pattern of FDOM, playing an important role in the dynamics of FDOM from the North area of the GoC through the persistent low-salinity Eastern North Atlantic Central Water. The oceanographic dynamics and the spatial pattern of FDOM concentration in the continental shelf of the GoC suggest a net transport of FDOM through the GCC (Gulf of Cadiz Current) to the Mediterranean Sea.

Annual variations of total and fractionated chlorophyll and phytoplankton groups in the Gulf of Cadiz.

Chlorophyll and phytoplankton distribution and concentration in the Gulf of Cadiz were studied during 2014 and 2015. In both years the highest chlorophyll concentrations are found at coastal stations during spring. Pico- and nanophytoplankton are the main contributors to total chlorophyll, with highest concentrations at the outer limit of the continental shelf. Microphytoplankton is responsible for most of the inshore chlorophyll. Picophytoplankton was analyzed to determine density, biomass and distribution. Prochlorococcus and Synechococcus show differences in distribution depending on distance from the coast and depth. Our results suggest temperature and consequent water stratification seem to be the main factors determining deep fluorescence maxima (DFM), mainly formed by picophytoplankton, especially Prochlorococcus. Pigment identification assisted by CHEMTAX analysis was carried out to analyze relative concentrations of larger phytoplankton.

Distribution of N2O in the eastern shelf of the Gulf of Cadiz (SW Iberian Peninsula).

Distribution of N2O has been determined in eight cruises along three transects (Guadalquivir, Sancti Petri and Trafalgar) in the Gulf of Cadiz, during 2014 and 2015. The mean N2O value for this area was 10.0±0.9nM, with large spatial and temporal variations. Stratification in the water column has been observed; the concentration of this gas increases with the depth, because of the presence of the Eastern North Atlantic Central Water (ENACW) and the Mediterranean Outflow Waters (MOW). The N2O production measured in this study is mainly due to nitrification. N2O yields from nitrification were estimated from the linear correlation of the excess of N2O (ΔN2O) with Apparent Oxygen Utilization (AOU) and nitrate (NO3-), with values of their slopes ranged between 0.010 and 0.021% and 0.017-0.025% respectively. There is an onshore - offshore gradient of N2O; the highest values were found at the shallower stations, indicating coastal input and benthic remineralization. The seawater-air flux of N2O is affected by several variables (temperature, AOU and NO3-), and the average flux calculated is 2.7±2.0µmolm-2d-1. The fluxes show a decrease with increasing distance from the coast, and with proximity to the Strait of Gibraltar. The study area behaves as a source of N2O to the atmosphere, with a global emission of 0.18Ggyear-1.

Spatial and seasonal variability of CH4 in the eastern Gulf of Cadiz (SW Iberian Peninsula).

Methane (CH4) concentrations were measured along three sections of the eastern Gulf of Cadiz (designated "Guadalquivir", "Sancti Petri" and "Trafalgar") during eight cruises in 2014 and 2015. The concentration of CH4 varied from 3.6 to 19.7nmolkg-1 (CH4 saturation percent of 122 and 916%), showing seasonal variation. The highest values were found in December 2014 and November 2015. In most of the sampling area the highest concentration of CH4 was found in subsurface waters at depths close to the thermocline, and in the bottom waters near the coast. The seawater-air flux of CH4 ranged between 0.8 and 59.7µmolm-2d-1, showing seasonal variation in function of the temperature of the surface water. In the "Guadalquivir" and "Sancti Petri" sections, the CH4 fluxes increased with proximity to the coast; this may be a result of continental inputs and CH4 emissions from sediments. The whole study area behaves as a source of CH4 to the atmosphere with mean values of 0.5 and 0.6GgCH4yr-1 in 2014 and 2015, respectively.

Anthropogenic effects on greenhouse gas (CH4 and N2O) emissions in the Guadalete River Estuary (SW Spain).

Coastal areas are subject to a great anthropogenic pressure because more than half of the world's population lives in its vicinity causing organic matter inputs, which intensifies greenhouse gas emissions into the atmosphere. Dissolved concentrations of CH4 and N2O have been measured seasonally during 2013 in the Guadalete River Estuary, which flows into the Cadiz Bay (southwestern Spanish coast). It has been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct discharges from nearby agriculture crop. Eight sampling stations have been established along 18 km of the estuary. CH4 and N2O were measured using a gas chromatograph connected to an equilibration system. Additional parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well, in order to understand the relationship between physicochemical and biological processes. Gas concentrations increased from the River mouth toward the inner part, closer to the wastewater treatment plant discharge. Values varied widely within 21.8 and 3483.4 nM for CH4 and between 9.7 and 147.6 nM for N2O. Greenhouse gas seasonal variations were large influenced by the precipitation regime, masking the temperature influence. The Guadatete Estuary acted as a greenhouse gas source along the year, with mean fluxes of 495.7 µmol m(-2)d(-1) and 92.8 µmol m(-2)d(-1) for CH4 and N2O, respectively.

Aerobic biodegradation of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids for different salinity values by means of continuous assays.

Aerobic biodegradation of linear alkylbenzene sulfonates (LAS) and sulfophenylcarboxylic acids (SPCs) in water, at different salinity values, has been studied. Three experiments have been carried out employing a staircase model system with continuous dosage of LAS to the system and using concentrations of LAS of the same order as those detected in littoral waters receiving urban wastewater discharges. LAS biodegradation was observed to be almost complete (showing a great extent), and in all cases exceeds 98.4%. At the very low concentration values of LAS utilized in the experiments, no significant variations in the biodegradation of LAS due to the effect of the different salinity values assayed were observed. The biodegradation intermediates detected for all the cases were sulfophenylcarboxylic acids with carboxylic chains of between five and 13 carbon atoms. The detection of C13-SPC (which is only produced by C13-LAS) confirms the existence of omega-oxidation. The total disappearance of SPCs in all cases indicates that mineralization of LAS at the concentrations tested was complete.

Toxicity of copper in natural marine picoplankton populations.

Standard microalgae toxicity tests should be able to establish responses in real ecosystems. Natural marine picoplankton samples collected during the months of March, June, August, October 2007 and January 2008, where exposed to 72 h copper toxicity tests. Results analysed by flow cytometry distinguished two groups, with different cytometric characteristics that can match with two of Synechococcus populations. EC(50) values for these two populations resulted low, ranging from 0.62 to 26.28 microg L(-1), this converts copper in a very powerful contaminant and Synechococcus in one of the most sensitive groups of phytoplankton. Differences in EC(50) values for a same population can be related to the month of collection including different initial cellular densities and oceanographic parameters that can affect the picoplankton's tolerance and distribution.

A multivariate assessment of sediment contamination in dredged materials from Spanish ports.

This paper summarises the performance of simple multivariate exploratory analyses to investigate on their potential application for dredged material characterization and management. The data from 25 sampling stations located at 7 different Spanish ports, produced a matrix consisting of 300 observations on 10 variables: the metals Cd, Cu, Cr, Hg, Ni, Pb and Zn, the metalloid As, the sum of PAHs and PCB congeners, and the proportion of fines and organic matter content. The cluster analysis was suitable to separate the sediments according to the extent of contamination while the PCA indicated that the data was defined by two principal factors: a first one that accounts for 56.4% of the total variance, describing the metallic contaminants except Ni and Cr, and a second one that accounts for 14.4% of the total variance describing the organic contaminants PAHs and PCBs. The use of these two simple and untutored multivariate techniques seems a cost-effective approach for future pre-dredging investigations in the studied areas providing useful information for dredged material characterization and management with little additional effort.

Effect of linear alkylbenzene sulfonate (LAS) and atrazine on marine microalgae.

Five marine microalgae (Tetraselmis chuii, Rhodomonas salina, Chaetoceros sp., Isochrysis galbana (T-iso) and Nannochloropsis gaditana), in the same biovolume quantity, were exposed to 72h growth-inhibition tests with atrazine and LAS. In all cases, the inhibition effect of atrazine was higher than that of LAS up to two orders of magnitude higher in the case of T. chuii. In a second part of the study, initial cellular densities for each microalga strain and fixed organic compound concentration were varied, and results show density has a clear influence in growth inhibition tests. Finally, the sum of all data obtained in the study was expressed in terms of "toxic cellular quota" (mass of chemical substance per cell). The result was a sigmoid curve with a good fit, including the two main factors in toxicity tests, initial cellular density and contaminant concentration. This toxic cellular quota exhibits a general tendency to increase with cell volume/size.

Direct comparison of amphipod sensitivities to dredged sediments from Spanish ports.

The sensitivity of the benthic amphipod species Ampelisca brevicornis and Corophium volutator to dredged sediments was compared through simultaneous testing on the standard 10 days sediment toxicity test. The results of mortality obtained for 22 harbor sediments sampled at several Spanish ports were studied together with the physico-chemical characteristics of the samples to obtain the incidence of toxicity in terms of dredged material categories and to identify possible differences in the amphipod mortality results when using one or another test species. The results showed a similar incidence of toxicity for medium-high and highly contaminated sediments for both amphipod species, similar to that obtained through the comparison of the chemical concentrations measured in sediments with the single limit values used in Spain for dredged material characterization and management. On the contrary, C. volutator presented a higher mortality and a higher incidence of toxicity when exposed to low and medium-low contaminated sediments, which may have been caused by the lower sensitivity of A. brevicornis when exposed to sediments from its natural environment. When compared to other amphipod species used for whole sediment toxicity assessment, both amphipod species used in this study reported slightly higher sensitivities although these differences could have been associated to the different set of chemical compounds considered when characterizing the sediment samples. In this sense, the amphipod mortality results were better predicted through the use of mean quotients than just by comparing the measured chemical concentrations with the single limit values used in Spain, which indicates that the toxic response of both species was caused by the cocktail of contaminants present in the sediments. Finally, the correlation analysis identified a higher association between A. brevicornis mortality and the metallic contaminants while C. volutator was more correlated with the organic micro-pollutants. Despite these differences, the results indicate that Ampelisca brevicornis can be used as test organism for dredged material characterization when enough individuals of other recommended species such as Corophium volutator are not available.

Liquid versus solid phase bioassays for dredged material toxicity assessment.

Since 1994 the results of the analyses of key chemical compounds (trace metals, polychlorinated biphenyls and polycyclic aromatic hydrocarbons) and the comparison with the corresponding sediment quality guidelines (SQGs) are used in decision-making for dredged material management in Spain. Nonetheless in the last decades a tiered testing approach is promoted for assessing the physical and chemical characteristics of dredged sediments and their potential biological effects in the environment. Bioassays have been used for sediment toxicity assessment in Spain but few or no experiences are reported on harbour sediments. We studied the incidence of toxicity in the 7 d bioassay using rotifers (Brachionus plicatilis) and the 48 h bioassay using sea urchin (Paracentrotus lividus) embryos over a series of experiments employing 22 different elutriates. The relative performance of this exposure phase was not comparable to data on the 10-d acute toxicity test using the burrowing amphipod Corophium volutator and the polychaete Arenicola marina, carried out on the whole sediments. These results evidence the importance of the exposure route and the test selected in decision-making, as the toxicity registered for the undiluted elutriates was largely due to the different solubility of sediment-bound contaminants. This work and other studies indicate that for many sediments, a complete battery of test is recommended together with physico-chemical analyses to decide whether dredged sediments are suitable for open water disposal or not.

Simulating a heavy metal spill under estuarine conditions: effects on the clam Scrobicularia plana.

We describe the effect of heavy metals Zn, Cd, Pb and Cu on the induction of methallothioneins on the clam Scrobicularia plana along a salinity gradient simulated under laboratory conditions. The clams were exposed to constant heavy metal concentrations in a dynamic estuary simulator during a 15-day assay to investigate possible induction of metal-binding proteins in them. The concentration of heavy metals in water was analysed. Clams were analysed for methallothionein concentrations. The speciation of Zn, Cd, Pb and Cu along the salinity gradient was modelled. Zn showed the highest concentrations and its prevalent species was the free ion. Intersite differences have been observed in methallothionein concentration and related to the salinity gradient. It seems that synthesis of methallothioneins is the result of physiological forces acting in concert with the changes in the chemical speciation of metals, owing to the trace metals uptake is controlled by means of an interaction of physiology and physicochemistry.

Sediment quality in the Guadalquivir estuary: lethal effects associated with the Aznalcóllar mining spill.

Monitoring from 1998 to 2001 has assessed the impact of the Aznalcóllar mining spill on the sediment quality in the Guadalquivir estuary. Chemical analysis has been completed with biological effects measured in different organisms. The toxicity of sediments obtained from dilutions of toxic mud and from environmental stations affected by the accidental spill was tested using the amphipod Ampelisca brevicornis and the clam Scrobicularia plana. The results obtained show that amphipods are more sensitive to the accidental spill than the clams. A dilution of clean sediment by more than 1.8% of toxic mud produced 100% mortality of amphipods. In GR2 station is detected toxicity to amphipods but not to clams. The rest of the environmental stations show no toxicity. Toxicity to amphipods in GR2 station decreased along time (from 50% to 60% of mortality in 1998 to 10 to 15% in 2001) and it can be associated with a recovery of the areas impacted by the accidental spill.

Sediment quality in the Guadalquivir estuary: sublethal effects associated with the Aznalcóllar mining spill.

As a complementary assessment of the impact of the Aznalcóllar mining spill on the Guadalquivir estuary two different sediment toxicity tests using fish (Solea senegalensis) and clams (Scrobicularia plana) were performed. The histopathological alterations by recording lesions at 15 and 30 days in fish to the gills, liver, gut and kidney and at 14 days in clams to the gills and gut were used to determine the adverse effects associated with the contaminants bound to sediments. The lesions measured at different tissues in both organisms show that the enrichment of heavy metals from the mining spill stressed some areas in the ecosystem of the estuary. The comparison of these effects with those lethal effects detected in the same samples using a multivariate analysis approach permits to identify the adverse effects associated with the accidental spill on the estuary. The incidence of the impact, located in specific areas of the estuary show an acute effect related to the spill.

The behaviour of heavy metals from the Guadalquivir estuary after the Aznalcóllar mining spill: field and laboratory surveys.

The spill at 'Los Frailes' caused a large input of metals into the riverine, estuarine and coastal ecosystems. Metal behaviour in natural waters can be studied both by performing field measurements, and by undertaking laboratory simulation experiments. Here is described the behaviour of the heavy metals Zn, Cd, Pb and Cu in the Guadalquivir estuary using incubation experiments and the results compared to those obtained during field assessments. If the toxic waste water had been discharged untreated into the environment, it could have raised the heavy metal concentrations in the estuary water to high values, such as 20.65 microM for Zn and 40 x 10(-3) microM for Cd. These values are several times higher than those obtained in samples collected in the area during the monitoring of the early impact. The metals present a non-conservative behaviour, with a high loss to waters of low salinity values.