Isotopes of nitrate and gadolinium fingerprints to assay human inputs in Guarani Aquifer System.

The use of environmental tracers brings comprehensive benefits to the management of water resources since it helps to prevent their pollution, minimize public health risks, and thus reduce the impact of urbanization. In Brazil, the Guarani Aquifer System (GAS) has strategic and environmental importance, making its preservation and sustainable exploitation mandatory. The present study aimed at evaluating sources of contamination in the GAS using the combination of geochemical data and two environmental tracers: nitrate isotopes (15NNO3 and 18ONO3) and one rare earth element (Gadolinium-Gd). For that, five wells-four exploiting the GAS and one the Bauru Aquifer System (BAS)-were selected to discuss the human inputs in groundwater used for public supply in an urban area. Traditional physicochemical analyses were conducted for six campaign samplings and nitrate monitoring for this period was evaluated on a time scale, also considering the accumulated rainfall. Besides that, the double isotopic method (DIM), e.g., δ18ONO3 e δ15NNO3, was applied to identify the fractionation and enable the distinction of the nitrate contamination source. In addition, the determination of anomalies of Gd, a wastewater-derived contaminant, was also performed to verify recent human inputs in groundwater. The results show that the local existence of nitrate in the GAS and BAS-even at low concentrations (values from 0.26 to 6.68 mg L-1)-originated from anthropogenic inputs (septic waste), as indicates the typical isotopic signals ratio in the isotopic approach. Associated with that, the evaluation of Gd permitted the separation of groundwater samples into older or more recent leakages. The use of environmental tracers to assess anthropogenic inputs in groundwater reiterates the importance of adopting more effective protection strategies for water resources management systems, in order to prevent contamination.

Anthropogenic gadolinium anomalies and rare earth elements in the water of Atibaia River and Anhumas Creek, Southeast Brazil.

The concentrations of rare earth elements (REE), measured in water samples from Atibaia River and its tributary Anhumas Creek, Brazil, present excess of dissolved gadolinium. Such anthropogenic anomalies of Gd in water, already described in other parts of the world, result from the use of stable and soluble Gd chelates as contrast agents in magnetic resonance imaging. Atibaia River constitutes the main water supply of Campinas Metropolitan area, and its basin receives wastewater effluents. The REE concentrations in water samples were determined in 0.22-µm pore size filtered samples, without and after preconcentration by solid-phase extraction with bis-(2-ethyl-hexyl)-phosphate. This preconcentration method was unable to retain the anthropogenic Gd quantitatively. The probable reason is that the Gd chelates dissociate slowly in acidic media to produce the free ion that is retained by the phosphate ester. Strong correlations between Gd and constituents or parameters associated with effluents confirmed the source of most Gd in water samples as anthropogenic. The shale-normalized REE patterns of Atibaia River and Anhumas Creek water samples showed light and heavy REE enrichment trends, respectively. Also, positive Ce anomalies in many Atibaia River samples, as well as the strong correlations of the REE (except Gd) with terrigenous elements, imply that inorganic colloidal particles contributed to the REE measured values.

Bioaccessible lead in soils, slag, and mine wastes from an abandoned mining district in Brazil.

We determined the amount of bioaccessible lead in samples of contaminated soils and in mining and refining wastes collected in the surroundings of a former smelter in a rural area in southeastern Brazil. Previous studies showed that some resident children and adults had blood Pb levels above recommended limits, but the contamination route was not established. The incidental ingestion of contaminated soils and dusts is considered to be a major route of lead uptake by humans. Bioavailability of heavy metals like Pb depends on solubility during digestion. We used in vitro tests that simulate human gastrointestinal (GI) media to measure the amount of soluble Pb under such conditions. Pb in soil and solid waste samples ranged from 0.03 to 4.1% and 1.2 to 15%, respectively. On average, 70% of the lead content was soluble in three different simulated gastric solutions (pH 1.5 and 1.7). For the same samples, lead solubility decreased to 2-22% when the pH was raised to pH 7 to approximate conditions found in the small intestine. These results indicate that if soils and dusts of the area are ingested, most of the lead will dissolve in the stomach, and part of it will remain soluble in the duodenum, i.e., would be potentially available for absorption. These findings may explain the high blood Pb levels previously reported.

Biogeochemical dynamics following land use change from forest to pasture in a humid tropical area (Rondjnia, Brazil): a multi-element approach by means of XRF-spectroscopy.

Forest burning for pastures in tropical areas represents an important component of biogeochemical cycles. In order to provide information concerning chemical modifications after forest burning, in this local study the total contents of 29 elements in topsoils were analyzed when forest is changed to pasture land. The work was carried out in 1999 in Rondjnia state (Brazilian Amazon Basin) focussing on a native forest site and four neighboring pastures established in 1987, 1983, 1972 and 1911 after forest conversion. Chemical fingerprint graphs of the pasture soils related to the forest soil illustrated mainly higher contents for the vast majority of macro- and micro nutrients, but for other elements as well (e.g. Ba, Sr, Cr, Ni, V or Pb). Also increases of pH levels were measured in all pastures, which remained higher than the forest values for decades. After initial increases of most of the elements in pasture of 1987 the decreases of some macro elements (e.g. C, N, K, Mg, S) in pasture 1983 as well as again the enhanced levels in pasture 1972 and 1911 suggest both a persistent leaching of these elements and a function of pasture age where external element inputs exceed outputs. Ash deposition, accumulation of organic matter, animal excreta as well as natural soil conditions are discussed as influencing factors on the element contents of the original forest and the pasture soils. Nevertheless, in this particular area continuous pasturing after forest clearing primarily enriched the soils in elements.