Human health risk assessment of metals and arsenic via consumption of commercial bivalves in the Gulf of California, Mexico.

Although various studies have reported the bioaccumulation of metals in bivalves of commercial interest from the Gulf of California (GC), the risk associated with their consumption remains poorly understood. In this study, our own and bibliographic concentrations of 14 elements in 16 species of bivalves from 23 locations were used to investigate (1) the species-specific and regional accumulation of metals and arsenic in bivalves, (2) the human health risks by age and sex, and (3) the maximum allowable consumption rates (CRlim). The assessments were done according to the US Environmental Protection Agency guidelines. The results indicate that the bioaccumulation of elements varies markedly between groups (oysters > mussels > clams) and localities (higher on Sinaloa due to intense anthropogenic activities). However, consuming bivalves from the GC remains safe for human health. To prevent health effects for residents or consumers on the GC, we recommend (1) following the CRlim proposed herein; (2) monitoring levels of Cd, Pb, and As (inorganic) in bivalves, as the elements of top concern, mainly when are consumed by children; (3) calculating CRlim for more species and locations, including at least: As, Al, Cd, Cu, Fe, Mn, Pb, and Zn; and (4) determine the regional consumption rates of bivalves.

Contrasting reproductive health of female clams Megapitaria squalida from two nearby metal-polluted sites in the Gulf of California: Potential effects of copper, lead, and cobalt.

We studied the effects of chronic exposure to metals on energy reserves and reproduction in the clam Megapitaria squalida in two nearby populations exposed to different levels of pollution from mining operations in the Gulf of California, Mexico. Female M. squalida from San Lucas beach had good reproductive health status, whereas Santa Rosalia specimens consistently showed low energy reserves, massive oocyte resorption throughout the year, high frequencies of undifferentiated individuals, low proportions of ripe and spawning organisms, smaller and fewer oocytes per follicle, and significantly lower follicular areas. Ovarian levels of Co, Cu, Pb, Mn, and Zn were consistently higher in clams from Santa Rosalia. The poor reproductive health of clams inhabiting this site may be attributed to their long-term exposure to high Co, Cu, and Pb concentrations, as these have been shown to cause toxicity and reproductive impairments in other marine organisms.

Vertical variability of benthic foraminifera and trace elements in a tropical coastal lagoon in the Gulf of California.

Population growth around water bodies is deteriorating environmental quality. The benthic foraminiferal and trace element concentration in a pair of short sediment cores were used to establish the quality of the sedimentary environment in a tropical coastal lagoon in the southwestern Gulf of California. From 25 cm depth towards the surface of the sediment core, Ammonia beccarii was dominant over nontolerant species and the concentrations of V, Ni, Co, Zn, Cu, Hg and Pb in the sediments increased compared with the lower depth intervals. This finding suggests a deterioration in the environmental quality of the lagoon since 1980, associated with an increase in the sizes of the population and vehicle fleet in the city of La Paz, Baja California Sur, and with the operation of three fossil fuel-based thermoelectric plants since 1985.

Abundance and distribution of benthic foraminifera as indicators of the quality of the sedimentary environment in a subtropical lagoon, Gulf of California.

Abundance and spatial distribution of benthic foraminifera were used to evaluate the impacts of anthropogenic activities on sediment quality in a coastal lagoon in the Gulf of California. In 1985 and 2013, 27 samples of superficial sediments were collected. The foraminifera genera Ammonia, Cribroelphidium, Quinqueloculina and Peneroplis were dominant in both years. The abundance of Ammonia increased from 41% to 60%, while Peneroplis abundance decreased from a maximum of 50% in 1985 to 7% in 2013. The greater abundance of Ammonia and the greater spatial coverage of Ammonia and Cribroelphidium suggest a marked environmental deterioration in the quality of the sedimentary environment, which contrasts with studies of trace elements in the sediment of this lagoon. The Foram Stress Index indicates that sediment quality has deteriorated over time, likely due to the effects of anthropogenic activities around the lagoon.

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.

Bioaccumulation and biomagnification of potentially toxic elements in the octopus Octopus hubbsorum from the Gulf of California.

The concentrations of 21 potentially toxic elements (PTEs) were determined in the tissues of Octopus hubbsorum from three locations along the Gulf of California coast: two near Santa Rosalia (SR), a site with historical metal contamination, and one in La Paz Bay, a reference site. Concentrations of Cd, Co, Cr, Mn, Ni, Pb, and Zn in octopus from the two SR sites were higher than those from the reference site, reflecting the higher sediment concentrations at the mining-impacted locations. The highest bioaccumulation and biomagnification of elements was found in digestive gland and branchial hearts, while the lowest was observed in the mantle, where the mean concentration of PTEs did not exceed international standards for human consumption of octopus. This study found elevated PTEs in octopus from sites with high metal contamination, and presents the first data on these elements in octopus from the Gulf of California.

Trace Elements in the Marine Sediments of the La Paz Lagoon, Baja California Peninsula, Mexico: Pollution Status in 2013.

To determine the actual concentrations of trace elements in surface sediments from the La Paz Lagoon, as well as their associations and possible origins, 91 sediment samples were analyzed for more than 50 elements using a combination of ICP-MS and ICP-AES. The results of a principal component analysis are used to distinguish four associative groups within the elements. Natural enrichment of As, Cd and U occurs due to the supply of weathered phosphorites from the El Cien formation located to the north-west of the lagoon. Sediment quality indices for potentially toxic trace elements do not show any probable impact on the biota of the lagoon. Only the concentrations of As in 30 % of the stations and Cu in 20 % of them exceed related effect range low levels. The highest concentration of Pb (36.8 mg kg(-1)) was measured in the sediments near the City of La Paz.

High heat flow and ocean acidification at a nascent rift in the northern Gulf of California.

The prevailing tectonic setting in the Gulf California suggests the presence of an undetermined number of short spreading centres with associated hydrothermal systems. However, to date, active seafloor spreading phenomena have been documented in only three of the eight tectonically active basins. Here we report heat flow values as high as 15,436 mW m(-2) in two of the northernmost basins of the Gulf of California, providing evidence of intense hydrothermal activity associated with the transition from continental rifting to seafloor spreading. The mean heat flow for the Wagner and Consag basins area is 1,875 mW m(-2), more than 15 times higher than the mean value for oceanic crust (105.4 mW m(-2)). Additional evidence for vigorous hydrothermal circulation and a shallow heat source includes intense gas discharge (CO(2) and CH(4)), widespread low pH (average 7.7), locally high (222)Rn concentrations in the bottom water and a high extent of organic matter maturation in the sediments.

Anthropogenic contamination of metals in sediments of the Santa Rosalía harbor, Baja California peninsula.

To know the environment impact on a harbor of the Santa Rosalía port on the Baja California peninsula, the concentrations of metals (Cd, Co, Cu, Mn, Pb, U and Zn) in harbor sediments were determined for 13 stations and compared with their average upper Earth´s crust abundance. The mean enrichment factors, calculated using Al as a normalizer, were higher than the unity for Ag, Ba, Bi, Cd, Co, Cu, Mn, Ni, Pb, Sb, U, V and Zn. Concentrations of slightly enriched Cd in the sediments are below the effect range low (ERL) sediment quality guidelines value only at three stations. The levels of Pb in the harbor sediments at four stations (1, 6, 9 and 11) are between the ERL (46.7 mg kg(-1)) and the effect range medium (ERM) (218 mg kg(-1)), and Pb content in the rest of the sediment samples is higher than the ERM, demonstrating the high extent of the anthropogenic impact of this metal on the sedimentary environment. The total concentrations of the potentially toxic elements Cu (3,390 ± 804 mg kg(-1)) and Zn (1,916 ± 749 mg kg(-1)) very strongly exceed their ERM, showing a high possibility of toxicological danger for marine biota, living inside or entering the harbor.

The impact of marine shallow-water hydrothermal venting on arsenic and mercury accumulation by seaweed Sargassum sinicola in Concepcion Bay, Gulf of California.

The influence of hydrothermal venting activity on arsenic (As) and mercury (Hg) accumulation was investigated in the shallow-water marine ecosystem of Concepcion Bay in the western Gulf of California. Geochemical data indicate that the marine shallow-water hydrothermal system of the Mapachitos site is a source of As and Hg for the water, sediment and algae collected along a transect moving across the western region of the bay. Although a small proportion of As and Hg precipitates close to the hydrothermal vent, both elements remain largely in the dissolved fraction, spreading a long distance from the source. The brown seaweed Sargassum sinicola thriving near the area of hydrothermal venting accumulates large quantities of As (above 600 mg kg (-1)), surpassing its typical concentration in the genus Sargassum by an order of magnitude. In contrast to As, the seaweed does not significantly accumulate Hg.

Anthropogenic and authigenic uranium in marine sediments of the central Gulf of California adjacent to the Santa Rosalía mining region.

To investigate the causes of uranium (U) enrichment in marine sediments in the eastern sector of the Gulf of California, surface sediments and sediment cores were collected adjacent to the Santa Rosalía copper mining region in the Baja California peninsula. Three coastal sediment cores were found to display high concentrations of U (from 54.2 ± 7.3 mg kg(-1) to 110 ± 13 mg kg(-1)) exceeding those found in the deeper cores (1.36 ± 0.26 mg kg(-1) in the Guaymas Basin to 9.31 ± 3.03 mg kg(-1) in the SR63 core from the suboxic zone). The contribution of non-lithogenic U (estimated using scandium to normalize) to the total U content in sediments of three coastal cores varied from 97.2 ± 0.4 % to 98.82 % versus 49.8 ± 3 % (Guaymas Basin) to 84.2 ± 8.2 % (SR62 core) in the deeper cores. The U content record in a lead-210 ((210)Pb)-dated core had two peaks (in 1923 and 1967) corresponding to the history of ancient mining and smelting activities in Santa Rosalía.

Major and trace elements in zooplankton from the Northern Gulf of California during summer.

We report the distribution of major and trace element concentrations in epipelagic zooplankton collected in the Northern Gulf of California in August 2003. The Bray-Curtis index defined three element assemblages in zooplankton: (1) major metals, which included only two elements, Na (3.6-17.0%) and Ca (1.0-4.8%). Na had its highest concentrations in the shallow tidally mixed Upper Gulf, where high salinity, temperature, and zooplankton biomass (dominated by copepods) prevailed. Ca showed its highest concentrations south of Ballenas Channel, characterized by tidal mixing and convergence-induced upwelling, indicated by low sea-surface temperature, salinity, and zooplankton biomass; (2) Six biological essential elements, like Fe (80-9,100 mg kg(-1)) and Zn (20-2,570 mg kg(-1)), were detected in high concentrations in zooplankton collected near Guaymas Basin, which had high surface temperature and chlorophyll a concentrations. (3) Metals of terrigenous origin, such as Sc (0.01-1.4 mg kg(-1)) and Th (0.03-2.3 mg kg(-1)), and redox-sensitive metals, like Co (3-23.8 mg kg(-1)); this was the assemblage with the largest number of elements (15). Both types of elements of assemblage 3 had maximum concentrations in the cyclonic eddy that dominates the summer circulation in the Northern region. We concluded that sediment resuspension by tidal mixing in the Upper Gulf, upwelling south of Ballenas Channel, and the cyclonic eddy were key oceanographic features that affected the element concentrations of epipelagic zooplankton in the Northern Gulf of California. Oceanographic mechanisms such as these may contribute to element incorporation in marine organisms in other seas.

Assessment of geochemical mobility of metals in surface sediments of the Santa Rosalia mining region, Western Gulf of California.

To asses the geomobility of cadmium, copper, iron, manganese, nickel, lead, and zinc in marine sediments near the Santa Rosalía copper smelter, which is located on the eastern coast of the Baja California Peninsula, sequential leaching was applied to sediment samples containing different levels of Cu: (1) uncontaminated or slightly contaminated (<55 mg kg⁻¹ Cu); (2) moderately contaminated (55-500 mg kg⁻¹ Cu); and (3) heavily contaminated (>500 mg kg⁻¹ Cu). Concentrations of Cd, Cu, Fe, Mn, Ni, Pb, and Zn in four fractions of the leachate (mobile fraction F1, relatively mobile fraction F2, associated with organic matter/sulphides fraction F3, and residual fraction F4) were measured by atomic absorption spectrophotometry (AAS). The sediments with Cu concentration <500 mg kg⁻¹ displayed prevalence of mobile acid-leachable fraction F1 and reducible fraction F2 for Cd, Cu, Mn, and Pb, whereas the relative contribution of fraction F3 was relatively low for all of the examined metals. Residual fraction F4 was highest (>65%) for Fe and Ni because both metals are associated with the crystalline matrix of natural sediments. The sediments heavily contaminated with Cu (>500 mg kg⁻¹) had dramatically increased percentages of Cu, Mn, Pb, and Zn, ranging on average from 63 to 81%, in the residual fraction. In the case of Cu, for example, the relative abundances of this element in the different fractions of such sediments followed this sequence: residual fraction F4 (76 ± 5%) >absorbed form and carbonates fraction F1 (15 ± 5%) >Fe and Mn oxyhydroxides fraction F2 (5 ± 2%) >fraction associated with organic matter and sulphides F3 (4.5 ± 3.9%). Copper, Pb, and Zn contents in each geochemical fraction of all samples were compared with sediment-quality guideline values ("effects range low" [ERL] and "effects range medium" [ERM]) to assess their possible negative effects on biota. Copper contents in mobile fractions F1 and F2, which were moderately contaminated with Cu, were higher than ERL but lower than ERM guideline values. For heavily contaminated sediments, Zn contents of mobile fractions F1 and F2 were higher than ERL but lower than ERM guideline values. The Cu content of fraction F1 was higher than ERM guideline values, whereas for fractions F2 and F3 copper content was higher than ERL guidelines but still lower than ERM guideline values.

Arsenic and mercury contamination of sediments of geothermal springs, mangrove lagoon and the Santispac bight, Bahía Concepción, Baja California peninsula.

In order to find out the environmental impact on the coastal zone, the composition of sediments of the intertidal geothermal hot spring zone and adjacent area of Playa Santispac in the pristine Bahía Concepción (Baja California peninsula) was studied. High concentrations of As (13-111 mg kg⁻¹) and Hg (0.55-25.2 mg kg⁻¹) were found in the sediments of the geothermal sources. Arsenic and Hg concentrations decrease rapidly in the adjacent small mangrove lagoon sediments and reach background levels (0.7-2.6 mg kg⁻¹ and 6-60 µg kg⁻¹ respectively) in the marine sediments collected in front of Playa Santispac.

Urban activity and mercury contamination in estuarine and marine sediments (Southern Brazil).

The distribution of mercury in sediments of the Patos Lagoon estuary and nearby coastal marine deposits has been investigated for the period 1998-2008. Polluted urban soils and coastal reclamation fills are the principal sources of high mercury concentrations for shallow estuarine sediments. The shallow sediments that form near the urban area enter the navigation canal and are transported into the ocean. The mercury concentration in sediments of the navigation canal has considerably increased since 2004, due to intense reconstruction activity in the urban area. Periodic dredging of the canal strengthens the preconditions for coastal marine sediment contamination by mercury. However, this does not occur because the resuspended dredged sediments are significantly diluted by natural suspended particulate matter.

Mercury dispersal to arroyo and coastal sediments from abandoned copper mine operations, el Boléo, Baja California.

Evidence for mercury dispersal in an arid coastal region of central Baja California (Mexico) suggests that abandoned copper mining operations are a noticeable source of mercury in the environment. There is a generally elevated level of mercury in alluvium of arroyos throughout the mining district (0.14-0.18 mg kg(-1)). In the first several dozen meters surrounding two of the biggest mines, mercury levels range from 0.26 to 3.16 mg kg(-1), forming a halo of anomalously high concentrations. The coastal marine sediments, particularly those close to the copper smelter in the town of Santa Rosalía, also display some mercury enrichment.

Mercury contamination of soil as the result of long-term phosphate fertilizer production.

This study was aimed at determining the range and spatial distribution of mercury in a geographical area influenced by the emissions of phosphate fertilizers industries in Rio Grande, Brazil. The case study demonstrated that mercury concentrations in a fine fraction of the surface soil close to the fertilizer factory reached levels as high as 800 microg kg(-1). Increased mercury concentrations were detected up to 60 cm below the soil surface. Further, a significant impact of the elevated mercury levels was manifested in a 1-km zone around the factory. Technical grade sulfuric acid employed in superphosphate production is considered the principal source of this mercury contamination.

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine.

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Peña Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.