Miguel Angel Huerta-Diaz

Heavy metal geochemistry of saltmarsh soils from the Rı́a of Ortigueira (mafic and ultramafic areas, NW Iberian Peninsula)

Concentrations of Fe, Mn, Ni, Cu, Cr and Zn in their total, silicate, organic, reactive and pyrite fractions were determined in soils collected from the Ortigueira saltmarshes (Esteiro, Ladrido and Mera, NW Iberian Peninsula), from sediments of the Landoi and Esteiro Rivers, and from sludge generated by a nearby dunite mine. The Esteiro saltmarsh presented clear enrichments of the four metals studied (first 10 cm), especially of Ni and Cr, whose concentrations were among the highest. It is proposed that the elevated Cr and Ni levels found in the Esteiro saltmarsh were derived from recent contributions of the mine, which are partially discharged into the Landoi River. Total Cu and Zn concentrations were lower than the corresponding ones for Cr and Ni. Under suboxic conditions, Ni, Cr, Cu and Zn were mainly associated with the reactive fraction. Under anoxic conditions, Cu and Ni were associated mainly with the pyrite phase. Pyritic Zn and Cr concentrations were relatively low and similar in all three saltmarshes; however, where anoxic-sulfidic conditions prevailed these two metals were mainly associated with the reactive and organic fractions.

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.

Influence of a turbidite deposit on the extent of pyritization of iron, manganese and trace metals in sediments from the Guaymas Basin, Gulf of California (Mexico)

Abstract A core collected in the Guaymas Basin contained an organic-poor, Mn oxide-rich and (relatively) Fe oxide-rich turbidite layer that affected the distribution of Fe, Mn, C, S and trace metals. Results indicate that sediments not influenced by the turbidite layer achieved a 100% degree of pyritization and, by extension, that pyrite production is Fe-limited in these sediments. In contrast, the mud slide layer apparently supplied enough reactive Fe to transfer essentially 98% of the total S present at the base of the turbidite (17–19 cm) to the pyrite reservoir. C/S ratios showed rapid decreases with depth, from a high of 38 close to the sediment-water interface, to minimum values of 2.8 at the lower limit of the turbidite layer, a ratio equal to the average C/S value of normal marine modern sediments, where concentrations of organic C and pyrite supposedly have attained quasi-steady values. A significant part of the reactive Mn was associated with carbonates (41±12%) and, to a much lower degree, with pyrite (2.7±1.2%). The turbidite layer is currently showing a depletion of Mn relative to the host sediment. It is possible that Mn, a major metal constituent in these sediments, was initially present in high concentrations in the mud slide, but was eventually mobilized and transferred either to the water column or to the sediments immediately below the turbidite layer. Metals associated with this element probably followed the same path, affecting their incorporation into pyrite. The turbidite layer apparently affected the distribution of most of the trace metals associated with pyrite, except maybe Cd, Pb and, to a certain, extent Cr. However, Cu, Cr, Zn, Ni and Co were all found to be highly pyritized (>80%) in the sediments of the Guaymas Basin.

Trace metal enrichments in nearshore sediments and accumulation in mussels (Modiolus capax) along the eastern coast of Baja California, Mexico: Environmental status in 1995

The biogeochemistry of trace metals in nearshore sediments and mussel was studied at 15 stations along a 1000 km long transect paralleling the west coast of the Gulf of California (GOC). Total trace metal (Me) and enrichment factor (EF(Me)) values in sediments were low due to negligible anthropogenic influence in the region. Past copper mining, however, near Santa Rosalia caused concentrations of Pb, Mn, Co, Zn and Cu which were 10-3.3×10(3) times greater than the average for the rest of the transect. Mussels also showed relatively high trace metal concentrations at the Santa Rosalia stations, but the variability in the spatial distribution was low and had undefined trends. Our results show that, with the exception of Co and Cu, the contamination caused by the copper mine affected sediments to a greater extent than mussels.

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.

Concentrations of Calcium, Magnesium, Potassium, and Sodium in Wines from Mexico

High concentrations of calcium (Ca), magnesium (Mg), potassium (K), and sodium (Na) are often responsible for imparting a salty character in wines that is often described as a negative sensory attribute. The wines of Mexico have been described as salty; however, the origin of the salty character of these wines is unknown. The objective of this study was to evaluate the concentrations of Ca, Mg, K, and Na in wines from Mexico and compare them to those found in wines from other countries. In general, concentrations were higher in the wines from Mexico. Specifically, levels of Na in red and white wines from Mexico were two-to three-fold higher than those in wines from other wine-producing countries. Thus, it is likely that the salty character described in some Mexican wines is, in part, the result of high concentrations of ions, especially Na.

Calibration of handheld X-ray fluorescence (XRF) equipment for optimum determination of elemental concentrations in sediment samples

Handheld X-ray fluorescence spectrometers (XRFs) represent a more practical, efficient and economic tool to determine the elemental composition of solid inorganic and organic samples than conventional analytical techniques. The objective of this work was to demonstrate that handheld XRFs could be a precise, accurate and reliable tool to analyze up to 27 different elements. This objective was accomplished through the optimization of an empirical calibration curve that, in addition to include certified reference materials (CRM), it also introduced new approaches, such as the use of solid CRM mixtures and combinations of organic and inorganic matrices. These approaches significantly increased the number of calibration points and eliminated hiatuses in the calibration curve. Several factors were evaluated before construction of the calibration curve: incidence time of the X-ray beam, type of film through which the X-ray beams reach the samples, container type, minimum sample volume and sample moisture content. Results show that single elements can be analyzed with variable exposure times or, alternatively, multielemental analyses can be carried out with a constant exposure time (180s). Costs can be reduced by using Ziploc® bags as sample containers, but the number of measurable elements drops from 27 to 21, while the possibility of contamination increases.

Mercury and Cadmium Concentrations in Farmed Bluefin Tuna (Thunnus orientalis ) and the Suitability of Using the Caudal Peduncle Muscle Tissue as a Monitoring Tool

Three regions (cephalic, central, and caudal) of the dorsal and ventral muscle tissue (R1 through R6) and the caudal peduncle muscle tissue (CPMT) of 20 farmed bluefin tuna (Thunnus orientalis) were analyzed for mercury (Hg) and cadmium (Cd) concentrations. Region 1 (cephalic-ventral) had significantly lower concentrations of Hg but significantly higher concentrations of Cd than did the other regions. However, average metal concentrations of all regions (R1 through R6) were only 6% lower for Hg and were not significantly different for Cd from those in the CPMT. Therefore, the CPMT was used to monitor the concentrations of these two metals in more than 100 farmed tuna collected from July 2004 to January 2009 under the assumption that the Cd concentrations in the CPMT would be representative of the Cd concentration in the whole body and that the Hg concentrations would be, in the worst case, overestimated by approximately 6%. The Hg and Cd concentrations in these tuna were inversely related to the condition index, i.e., the tuna in better condition had the lowest concentrations of these metals. The mean concentrations in the CPMT of all fish analyzed were 0.31 ± 0.17 μg/g wet weight for Hg and 0.007 ± 0.006 μg/g wet weight for Cd. These concentrations were below the limits established by Mexican regulations for seafood (1.0 and 0.5 μg/g for Hg and Cd, respectively) and Japan (0.4 μg/g for Hg).

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.