Arsenic pollution in Patos Lagoon estuarine sediments, Brazil

Arsenic distribution in sediments of the Mirim-Patos lagoonal system is investigated. Deposits of fresh water Mirim Lagoon and those of the fresh water part of the Patos Lagoon contain 2.5 and 7.7 mg kg(-1), respectively, on average of total arsenic. In contrast, estuarine sediments of the Patos Lagoon are evidently contaminated by arsenic in high concentrations (up to 50 mg kg(-1)), and about 80% of the arsenic there is found in a bioavailable form. Analytical data coupled with direct, visual observations of estuarine water contamination by raw phosphorites and fertilizers suggest that the major source of arsenic in the estuarine sediments originated from the fertilizer industry.     

Mercury pollution sources in sediments of Patos Lagoon Estuary,Southern Brazil

Present study has continued the investigation on distribution of mercury in estuarine sediments of Patos Lagoon which began whilst assessing the after-effect of enormous accidental discharge of sulfuric acid into the estuary. An attempt to evaluate the contribution of anthropogenic effluents on mercury pollution in sediments was undertaken. The effluents from Rio Grande City sewages were categorized into four groups based on their sources. Comparison of mercury concentrations from those, indicated that domestic effluent was prevalent. Apparent geographic controls of effluent locations enriched in mercury on zones of polluted estuarine sediments were also revealed. Insufficient control on waste collecting and absence of sewage treatment are considered the principal causes of mercury pollution in estuarine sediments.     

Calcareous algae bioclast contribution to sediment enrichment by arsenic on the Brazilian subtropical coast

Arsenic levels (up to 130 mg kg⁻¹) substantially exceeding the official threshold have recently been documented in beach and nearshore sediments along more than 50 km of coastline in the Brazilian state of Espírito Santo between 19°50′ and 20°12′S. In an attempt to assess the sources of this enrichment, we performed a study on arsenic distribution in the main mineral substances and living organisms in the beach environment. Laboratory tests on arsenic retention by beach carbonate debris have also been carried out. The data suggest that sedimentary arsenic occurs largely bound to particles of the calcareous red alga Corallina panizzoi, whereby live specimens contained much smaller amounts of this metalloid than was the case for nonliving material (2.4 and 20.3 mg kg⁻¹, respectively). Experimental tests confirmed the ability of C. panizzoi detritus to retain arsenic at pH intervals and ionic strength characteristic of seawater. There are two potential sources of that metalloid for calcareous debris in sediments: brown macroalgae, which were found to contain high levels of As (up to 66.3 mg kg⁻¹), and ferruginized sandstones (up to 23.0 mg kg⁻¹). We argue that any contribution of brown algae to beach sediment enrichment by As would be minor, and consider the ferrous sandstones from coastal sedimentary rocks of the Barreiras Group as the principal large-scale source of arsenic in the marine environment of Espírito Santo. The experimental data, together with field studies, corroborate the interpretation that arsenic anomalies in sediments with calcareous debris can form when weathered continental rocks even only slightly enriched in As are leached by marine waters, and the As is at least partially retained by biogenic calcareous detritus in nearshore sediments. Considering that rocks of the Barreiras Group are exposed to marine erosion far to the north of Espírito Santo, we estimate that marine sediments containing calcareous material are “anomalously” enriched in As along approximately 2,000 km of the Brazilian tropical coastline.     

The effect of accidental sulphuric acid leaking on metal distributions in estuarine sediment of Patos Lagoon.

In August of 1998 the tanker BAHAMAS belonging to the Chem Oil Company containing 12,000 t of concentrated sulphuric acid, had an accident on board, after which estuarine water entered one of the compartments of the tanker, resulting in a vigorous exothermic reaction. The reaction of acid with the metallic interior hull of the ship and the accompanying heat and H2 production resulted in an imminent risk of explosion. To avoid an explosion, given the fact that neutralization was not possible, some of the cargo was discharged into the surrounding water. Neutralization was done in January 1999, after the acid concentration in the tanker had decreased and the concentrations of Fe, Cr and Ni remained elevated. Metal concentrations in bottom sediments showed significant modifications. Leached mercury migrated and redeposited downstream, reaching approximately 76 times the background values. Such an anomaly has a well expressed barrier character. The mechanism for redeposition of Hg and other metals probably followed the pattern: Downstream as a result of dilution and mixing with seawater the pH of acid-water increases, favouring adsorption and/or precipitation of metals. The leading edge of a geochemical barrier, at positions 7-9 of sampling sites (Fig. 1), is confirmed by pH variations in the water. The reestablishment of normal pH occurred after a short time due to the high buffering capacity of seawater and large natural dilution process. The concentration of metals in estuarine water during and after the accident showed insignificant anomalies.     

Effects of Bioirrigation and Salinity on Arsenic Distributions in Ferruginous Concretions from Salt Marsh Sediment Cores (Southern Brazil)

Arsenic (As), iron (Fe), and manganese (Mn) contents were measured in sediment nodules and associated pore waters obtained from sediment cores collected from a salt marsh on Pólvora Island (southern Brazil). Sediment cores were obtained when brackish water dominated the estuary, at two different environments: an unvegetated mudflat colonized by crabs (Neohelice granulata), and a low intertidal stand vegetated by Spartina alterniflora. We determined the percentage of nodules in each depth interval of the cores, along with redox potential, and As, Fe, and Mn contents of the nodules. The mineralogy of the nodules was investigated, and results showed they are mainly composed by quartz, phyllosilicates, and amorphous Fe–Mn oxides/oxyhydroxides. Pore water results showed that bioturbation by local crabs supports oxygen penetration to depths of ca. 25 cm below the salt marsh surface, with lower Fe contents in pore water associated with the brackish period. However, S. alterniflora growth appears to have a greater impact on sediment geochemistry of Fe, Mn, and possibly As due to sulfate reduction and the associated decrease in pore water pH. Higher Fe concentrations were observed in the pore waters during the period of brackish water dominance, which also corresponded to the S. alterniflora growth season. The study demonstrates that differences in geochemical conditions (e.g., Fe content) that can develop in salt marsh sediments owing to different types of bioirrigation processes (i.e., bioirrigation driven by crabs versus that related to the growth of S. alterniflora) play important roles in the biogeochemical cycling of As.