Francisco Delgadillo-Hinojosa

Diagnosis of trace metal contamination in sediments : The example of Ensenada and El Sauzal, two harbors in Baja California, Mexico

Total metal concentrations in sediments from within Ensenada and El Sauzal Harbors are generally higher than at the mouths. Grain-size analyses suggested that this enrichment could be due to the presence of fine-grained sediments in the inner part of the harbors rather than to anthropogenic perturbations. The (Me/Al)sample ratios for Pb, Co, Ni and Fe were significantly higher for Ensenada Harbor relative to El Sauzal Harbor, whereas the ratios for Cd, Mn, Zn and Cu were statistically equivalent for both harbors. Calculated enrichment factors [EFMe=(Me/Al)sample/(Me/Al)shale] indicated that the metals showing slight enrichment were those associated with anthropogenic contamination (Pb, Zn), or probably related to primary productivity in the water column (Cd, Co). The levels of most of the metals were not greatly enriched, a consideration that is of the utmost importance when contamination issues are at stake.

Spatial distribution of copper in relation to recreational boating in a California shallow-water basin

The overall effect of the number of boats on the copper (Cu) levels in the water column and sediment, along with their spatial variability within Shelter Island Yacht Basin (SIYB), San Diego Bay, California was examined. We identified a horizontal gradient of increasing dissolved Cu and Cu in sediment from outside to the head of SIYB which was coincident with the increasing number of boats. Spatial models of Cu distribution in water and sediment indicated the presence of ‘hotspots’ of Cu concentration. From outside to the head of SIYB, dissolved Cu ranged from 1.3 μ g L−1 to 14.6 μ g L−1 in surface water, and 2.0 μ g L−1 to 10.2 μ g L−1 in bottom water. Cu in sediment exceeded the Effect Range Low of 34 mg kg−1 (i.e. where adverse effects to fauna may occur), with a peak concentration of 442 mg kg−1 at the head of the basin. Free Cu++ in surface water was several orders of magnitude higher than in sediment porewater. High-resolution data of Cu species together with probability maps presented in this paper will allow managers to easily visualise and localise areas of impaired quality and to prioritise which areas should be targeted to improve Cu-related conditions.

Copper Complexation Capacity in Surface Waters of the Venice Lagoon

Total copper (Cu(T)), copper ion activity (pCu) and the copper complexation capacity (CuCC) were determined in samples of seawater collected in July 2003 from the Venice Lagoon. Cu(T) and CuCC showed considerable spatial variability: Cu(T) ranged from 1.8 to 70.0nM, whereas the CuCC varied from 195 to 573nM. pCu values varied from 11.6 to 12.6 and are consistent with those previously reported in estuarine and coastal areas (10.9-14.1). The range of Cu(T) values compares well with those reported in the past in the lagoon and in the adjacent Adriatic Sea. The highest concentrations of Cu(T) were found in samples collected near the industrial area of Porto Marghera, whereas the lowest were measured near the Chioggia and Malamocco inlets, where an intense tidally-driven renewal of seawater takes place. Although CuCC showed a high degree of spatial variability, the values recorded in the Venice Lagoon are comparable to those reported in other estuarine systems. In addition, CuCC was positively correlated with dissolved organic carbon (DOC), suggesting that organic ligands responsible for Cu complexation are part of the bulk organic matter pool in the lagoon. The CuCC:Cu(T) molar ratio was, on average 55:1, indicating that a large excess of complexation capacity exists in the Venice Lagoon. The high levels of CuCC and the narrow range of pCu indicates the importance of the role played by organic ligands in controlling the free ion Cu concentrations in the lagoon, and as a consequence, regulating its availability and/or toxicity.

Millimeter-scale resolution of trace metal distributions in microbial mats from a hypersaline environment in Baja California, Mexico.

Microbial mats from two ponds with different salinities from the saltern of Guerrero Negro (Mexico) points toward millimeter-scale coherent variations in trace metal (Me) concentrations (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn). Total, HCl-leachable and pyrite-associated Me showed a trend of increasing concentrations with increasing depth suggesting gradual addition of reactive Me probably as a result of metal sulfide precipitation at depth. The trends in Me profiles can be ascribed to the establishment and maintenance of microzones that promote geochemical processes, bacterial population distributions, and differential mass transport within the mats. Degrees of trace metal pyritization (1 ± 1% for Zn to 24 ± 7% for Cd) as well as metals associated with the pyrite fraction (<1.4-36 ± 18 nmol g(-1) for Zn and Mn, respectively) were low, as expected from a reactive Fe-limited system like Guerrero Negro. Calculated enrichment factors showed that Ni (2.6 ± 2.1), Co (5.5 ± 4.0), Pb (9.4 ± 7.4), and Cd (57 ± 39) were, on average, enriched in the microbial mats of Guerrero Negro. Natural enrichments of Cd, Pb, and Co in sediments along the coast of Baja California and metabolical requirements of Co and Ni by the predominant cyanobacteria in the Guerrero Negro mats may explain these enrichments. Metal characteristics in microbial mats could be advantageously used as biosignatures to identify their presence in the geological record or in other planetary systems.

Cadmium and phosphate variability during algal blooms of the dinoflagellate Lingulodinium polyedrum in Todos Santos Bay, Baja California, Mexico.

Dinoflagellate algal blooms (DABs), with Lingulodinium polyedrum as the dominant species, have increased over the past few years in coastal areas off Baja California, Mexico. Vertical and temporal variability of particulate cadmium (Cdp), dissolved Cd (Cdd), PO4(3-) and Cdd/PO4(3-) were investigated during two intense DABs of L. polyedrum that occurred during the fall of 2011 and 2012 in Todos Santos Bay. Results were then, compared with data gathered in the absence of algal blooms during the autumn of 2013. In both algal blooms, L. polyedrum tended to be concentrated near the surface throughout the duration; however, during DAB 2011 the number of cells was twice as abundant ([10.0 ± 8.0] × 10(5) cells L(-1)) as in DAB 2012 ([5.0 ± 4.4] × 10(5) cells L(-1)). During DAB 2011, Cdp increased significantly (up to 1.02 ± 0.99 nmol kg(-1)) and was positively correlated with the cell abundance of L. polyedrum, suggesting that this dinoflagellate is able to assimilate and concentrate Cdd. Likewise, Cdd (up to 0.71 ± 0.17 nM) increased in the days of highest cell abundance, which could be attributed to uptake and subsequent regeneration of Cdd resulting from the remineralization of organic particulate matter produced during the bloom, as well as with the presence of organic ligands secreted by L. polyedrum that could keep Cdd in solution. During DAB 2011, dissolved Cdd/PO4(3-) ratios exhibited high vertical and temporal variability in the upper 5 m of the water column, but remained virtually constant near the bottom, suggesting a depth-dependent decoupling between these two dissolved components during the bloom development. Given the observed differences in the vertical and temporal variability of Cdd, Cdp, and PO4(3-) between these two intense DABs, we propose the existence of an abundance threshold of approximately 10(6) cells L(-1) of L. polyedrum above which Cd and PO4(3-) significantly increased due to remineralization in coastal waters during the bloom development.

Trace metals partitioning among different sedimentary mineral phases and the deposit-feeding polychaete Armandia brevis.

Trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) were determined in two operationally defined fractions (HCl and pyrite) in sediments from Ensenada and El Sauzal harbors (Mexico). The HCl fraction had significantly higher metal concentrations relative to the pyrite fraction in both harbors, underlining the weak tendency of most trace metals to associate with pyrite. Exceptionally, Cu was highly pyritized, with degrees of trace metal pyritization (DTMP) >80% in both harbors. Dissolved Fe flux measurements combined with solid phase Fe sulfide data indicated that 98 mt of Fe are precipitated as iron sulfides every year in Ensenada Harbor. These Fe sulfides (and associated trace metals) will remain preserved in the sediments, unless they are perturbed by dredging or sediment resuspension. Calculations indicate that dredging activities could export to the open ocean 0.20±0.13 to (0.30±0.56)×10(3) mt of Cd and Cu, respectively, creating a potential threat to marine benthic organisms. Degrees of pyritization (DOP) values in Ensenada and El Sauzal harbors were relatively low (<25%) while degrees of sulfidization (DOS) were high (~50%) because of the contribution of acid volatile sulfide. DOP values correlated with DTMP values (p≤0.001), indicating that metals are gradually incorporated into pyrite as this mineral is formed. Significant correlations were also found between DTMP values and -log(Ksp(MeS)/Ksp(pyr)) for both harbors, indicating that incorporation of trace metals into the pyrite phase is a function of the solubility product of the corresponding metal sulfide. The order in which elements were pyritized in both harbors was Zn≈Mn<Fe<Cd≈Pb<Ni≈Co<<Cu. Lastly, a strong correlation (r(2)=0.87, p<0.01) was found between average reactive trace metal concentrations and metal concentrations measured in Armandia brevis (a deposit-feeding Opheliid polychaete), suggesting that these labile sedimentary metals are preferentially accumulated by the polychaete, making it a useful biomonitor of sedimentary metal exposure.

Intertidal geothermal hot springs as a source of trace elements to the coastal zone: A case study from Bahía Concepción, Gulf of California

We investigated the influence of the intertidal geothermal hot spring (GHS) on the biogeochemistry of trace elements in Santispac Bight, Bahía Concepción (Gulf of California). The geothermal fluids were enriched in As and Hg mainly in ionic form. The suspended particulate matter of the GHS had elevated enrichment factor (EF) >1 of As, Bi, Cd, Co, Cu, Mn, Mo, Sb, Sn, Sr, Ti, U and Zn. The sediment core from GHS1 had high concentration of As, Hg, Corg, S, V, Mo, and U and the extremely high EF of these elements at 8cm of the core. The maximum bioaccumulation of As and Hg was in seaweeds Sargassum sinicola collected near the GHS2. The results confirm the input of trace elements to the coastal zone in Bahía Concepción from geothermal fluids and the evident modification of the chemical composition of the adjacent marine environment.

Atmospheric Inputs of Iron and Manganese to Coastal Waters of the Southern California Current System: Seasonality, Santa Ana Winds, and Biogeochemical Implications

The magnitude and temporal variability of mineral dust deposition and its associated Fe and Mn inputs to coastal waters of the California Current System (CCS) has been scarcely investigated. Here we report a 5 year time series (April 2010 to December 2014) of mineral dust (Fdust), Fe (FFe), and Mn (FMn) fluxes to the coastal zone of the southern CCS. Atmospheric deposition displayed a strong seasonal trend, with lowest Fdust, FFe, and FMn during the warm season (May–October), a period dominated by strong moisture-laden winds of oceanic origin. In contrast, the highest Fdust, FFe, and FMn were recorded during the cool season (November–April), a period characterized by strong winds devoid of moisture coming from the mainland. Our analysis suggests that Santa Ana Wind events could contribute with ∼15%, 20%, and 24%, respectively, to the total annual input of dust, Fe and Mn to the region. Besides, atmospheric soluble Fe inputs are equivalent to between 11% (warm season) and 35% (cool season) of the dissolved Fe supplied by upwelling. Our calculations indicate that atmospheric Fe deposition could explain between ∼5% (warm season) and 15% (cool season) of primary production reported for the southern CCS, suggesting that this route could also be an important input of Fe for primary producers in this region. Finally, the average Fdust, FFe, and FMn for the cool seasons showed a positive interannual trend that was significantly correlated with an intensification of drought conditions over the period 2010–2014 in northwest of Mexico and southwest of the United States.