Global deposition of potentially toxic metals via faecal material in seabird colonies.

Seabirds are known to play an important role in the geochemical cycling of macronutrients; however, their role in cycling elements of environmental interest has not been investigated. Guano is an important source of marine-derived nutrients and trace metals in seabird nesting areas, but most of the available information on this topic is derived from local studies. In the present study, we used a bioenergetic model to estimate the amounts of cadmium (Cd), mercury (Hg) and lead (Pb) that are deposited via faecal material in seabird colonies worldwide. The findings showed that the seabirds excreted 39.3 Mg (Mg = metric ton or 1000 kg) of Cd, 35.7 Mg of Hg and 27.2 Mg of Pb annually. These amounts are of the same order of magnitude as those reported for other fluxes considered in the geochemical cycling of these elements (e.g. sea-salt spray, cement production, soil loss to oceans). Most of the deposition occurs in circumpolar zones in both hemispheres and, interestingly, high proportions of the metals in the excrements occur in geochemically labile forms, which can be easily leached into coastal waters and assimilated by marine organisms.

Heavy metal concentrations in the Pacific sharpnose shark Rhizoprionodon longurio from the Santa Rosalia mining zone, Baja California Sur, Mexico.

Rhizoprionodon longurio is an important commercial species captured in an area with heavy metal presence due to the mining waste from Santa Rosalia, Gulf of California, and levels of heavy metals in its muscle remain unknown. This study aimed to investigate whether contamination levels are below the limits allowed for human consumption and to prevent health damage. Concentrations of essential (Cu, Fe, Mn, and Zn) and non-essential (Ag, Cd, and Pb) trace elements were determined in fifty-seven muscle samples of R. longurio. The average concentrations of Fe > Zn > Cu > Mn > Cd > Ag did not exceed the permissible limits for human consumption established by the Mexican norm, WHO, and FAO. The mineral daily ingestion was 0.10 to 0.53 % × 100 g of muscle, and the percentage of weekly consumption was 2.5 % to <12 % concerning corporal weight. The meat from this shark can be consumed due to its low toxic potential for human health.

Sediment trace metal levels in the Ojo de Liebre Lagoonal Complex (Baja California, Mexico), a marine wildlife protected area.

Surficial sediment quality in the Ojo de Liebre Lagoon (OLL), Mexico, was evaluated via five geochemical indices. Results indicate that concentrations of the elements Ag, As, Cu, Fe, Mn, Mo, Ni, Sb, U, V and Zn do not exert adverse biological effects in this ecosystem. However, minor enrichment was observed for Ba (mean ± SD: 1.09 ± 0.17) and Co (1.57 ± 0.22) and was moderately severe for Cd (9.3 ± 2.0), possibly due to natural processes. The adverse effect index was >1 only for Hg, suggesting that concentrations of this element are sufficiently high (0.40 to 1.13 nmol g-1) to potentially elicit adverse effects on local organisms in contact with sediments. This result is particularly important for grey whales (Eschrichtius robustus), given that they ingest large quantities of benthic organisms during their seasonal stay in the OLL.

Seabird colonies as important global drivers in the nitrogen and phosphorus cycles.

Seabirds drastically transform the environmental conditions of the sites where they establish their breeding colonies via soil, sediment, and water eutrophication (hereafter termed ornitheutrophication). Here, we report worldwide amounts of total nitrogen (N) and total phosphorus (P) excreted by seabirds using an inventory of global seabird populations applied to a bioenergetics model. We estimate these fluxes to be 591 Gg N y-1 and 99 Gg P y-1, respectively, with the Antarctic and Southern coasts receiving the highest N and P inputs. We show that these inputs are of similar magnitude to others considered in global N and P cycles, with concentrations per unit of surface area in seabird colonies among the highest measured on the Earth's surface. Finally, an important fraction of the total excreted N (72.5 Gg y-1) and P (21.8 Gg y-1) can be readily solubilized, increasing their short-term bioavailability in continental and coastal waters located near the seabird colonies.

Biosorption removal of benzene and toluene by three dried macroalgae at different ionic strength and temperatures: Algae biochemical composition and kinetics.

Release of low-molecular aromatic hydrocarbons (HC) into natural waters brings severe consequences to our environment. Unfortunately very limited information is available regarding the treatment of these pollutants. This work evaluated the use of brown, green and red macroalgae biomass as biosorbents of benzene and toluene, two of the most soluble HC. Raw seaweed biomasses were completely characterized, then evaluated under different temperatures and ionic strengths to assess their potential as biosorbents and to elucidate the biosorption mechanisms involved. Brown macroalgae registered the highest removal capacities for benzene and toluene (112 and 28 mg·g-1, respectively), and these were not affected at ionic strength < 0.6 M. Langmuir and Sips isotherm equations well described biosorption data, and the pseudo-second order model provided the best fit to the kinetics rate. Hydrocarbons are adsorbed onto the diverse chemical components of the cell wall by London forces and hydrophobic interactions.

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.

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

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.

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.