Vanessa Hatje

Determination of total arsenic and arsenic (III) in phosphate fertilizers and phosphate rocks by HG-AAS after multivariate optimization based on Box-Behnken design

In the present paper, a procedure for the determination of total arsenic and arsenic (III) in phosphate fertilizers and phosphate rocks by slurry sampling (SS) with hydride generation atomic absorption spectrometry (HG-AAS) is proposed. Arsenic (III) is determinated directly and total arsenic is determinated after reduction reaction. The procedure was optimized for the flow rate of NaBH(4), NaBH(4) and hydrochloric acid concentrations using a full two-level factorial and also a Box-Behnken design. Slurry preparation with hydrochloric acid in an ultrasonic bath allowed the determination of arsenic (III) with limits of detection and quantification of 0.1 and 0.3 microg L(-1), respectively. The precision of results, expressed as relative standard deviation (RSD), was always lower than 3%. The accuracy of this method was confirmed by analysis of certified sediment reference materials, while the procedure also allows for calibration using aqueous external standards. This method (SS/HG-AAS) was used to determine total arsenic and arsenic (III) in two phosphate rock samples and two phosphate fertilizer samples. In these samples, total arsenic concentrations varied from 5.2 to 20.0 mg kg(-1), while As (III) concentrations varied from 2.1 to 5.5 mg kg(-1), in agreement with published values. All samples were also analyzed using acid digestion/HG-AAS. Both, a paired t-test and a linear regression model demonstrated no significant difference (95% CL) between the results obtained using these two sample preparation procedures.

Influence of proximity to an urban center in the pattern of contamination by marine debris.

In order to test the relationship between the occurrence of marine debris and the distance from urban areas, nine beaches in the metropolitan area of Salvador, Bahia, Brazil and the adjacent northern coast were studied. Marine debris were collected, sorted in several categories and weighed. It was observed that plastics were numerically the most abundant component of the collected debris. As expected, the beaches closest to Salvador presented the largest density of debris, with the exception of the Porto da Barra beach, which has an efficient public cleaning system and does not have any vegetation, making it difficult to accumulate solid waste. Linear regression analyses showed significant relationships between the distance from the urban center (Salvador) and the number of marine debris per m(2), the total number of debris per beach (abundance), and the diversity of debris types (richness). The results showed that proximity to urban regions was a key factor in the marine debris distribution along the coast.

Integrated assessment of metal contamination in sediments from two tropical estuaries

In order to evaluate if sediment metal contamination is responsible for benthic degradation and identify possible reference sites in Todos os Santos Bay (TSB), comparisons between a highly impacted (Subaé) and less impacted (Jaguaripe) estuarine systems were made based on (i) field assessment of macrobenthic assemblage, (ii) sediment metal concentrations and (iii) chronic toxicity test with the tropical copepod Nitokra sp. Data were integrated by multivariate analysis (BIOENV and PCA) and the ratio-to-mean (RTMe) approach. Estuaries were divided into four different salinity zones to avoid misclassification of benthic conditions. Salinity was the main variable correlated to the benthic distribution in both estuaries, indicating that categories based on salinity features seem to be suitable in TSB. Correspondence among lines of evidence differed in low and high metal contaminated systems. Chronic toxicity was found along both the entire systems, being considerably higher in Jaguaripe. However, there was no clear evidence of metal contamination and benthic alteration in most stations of Jaguaripe. Although the concentrations of Sr and Cu were correlated to the benthic assemblage in Jaguaripe, it is unlikely that toxicity has been caused by these elements. The benthic assemblage distribution of Jaguaripe seems to be rather related to natural stressful conditions of transitional waters. Even though the Jaguaripe estuary might not be pristine, it can be used as a reference estuary for benthic assessment in TSB. Regarding the Subaé estuary, toxicity and Zn were also correlated to the benthic assemblage and most stations showed signs of benthic alteration and metal contamination. All lines of evidence were in agreement providing evidences that metal contamination might be responsible for benthic degradation in Subaé.

Overview of the 20th century impact of trace metal contamination in the estuaries of Todos os Santos Bay: Past, present and future scenarios

This paper discusses the distribution patterns of trace metals in sediments and suspended particulate matter (SPM) in the three main estuaries of the Todos os Santos Bay (BTS), Brazil, during dry and rainy seasons. Data available up to 2012 was also reviewed to assess the status of contamination. For most elements, metal concentrations in sediments decreased from the tidal limits to the lower estuary. Metals in SPM presented more complex distributions along the salinity gradient. Metal variability between rainy and dry conditions was only significant for SPM data. Of the BTS estuaries, the levels of Cd, Zn, Pb and Cu are highest in the Subaé estuary, and they seem to be promoting harmful biological effects in macrofauna, and also may pose potential human health risks. Despite the evidence of important localized contamination, much of the data compiled indicates that the bay and its estuaries are still relatively preserved.

Inorganic As speciation and bioavailability in estuarine sediments of Todos os Santos Bay, BA, Brazil.

The spatial distribution of As (total As, As (III) and As (V)) in estuarine sediments from the main tributaries of Todos os Santos Bay, BA, Brazil, was evaluated under high and low flow conditions. The concentrations of As were determined using a slurry sampling procedure with hydride generation atomic absorption spectrometry (HG-AAS). The highest concentrations were observed at estuary mouths, and exceeded conservative lower threshold value (Threshold Effects Level; TEL). Due to the oxic conditions and abundance of Mn and Fe (oxyhydr)oxides in the sediments, most inorganic arsenic in the Subaé and Paraguaçu estuaries was present as As (V). Nevertheless, the concentration of As (III) at several locations along the Jaguaripe River were also above the TEL value, suggesting that As may be toxic to biota. In the Subaé estuary, antropogenic activities are the main source of As. At the Jaguaripe and at Paraguaçu estuaries, nevertheless, natural sources of As need to be considered to explain the distribution patterns.

Shellfish from Todos os Santos Bay, Bahia, Brazil: treat or threat?

This study determined the concentrations of major and trace elements in shellfish (oysters, clams and mussels) and conducted an assessment of the health risks due to the consumption of contaminated seafood. Samples were collected at 34 sites along Todos os Santos Bay, Brazil. The elements were determined by ICP OES and Hg by Direct Mercury Analysis. Relatively high concentrations of trace elements (As, Zn, Se and Cu) were found in seafood tissues. Potential daily intake of As, Co, Se, Zn and Cu associated to shellfish consumption suggested relevant non-carcinogenic risk for all studied locations. Copper was the element that posed the greatest non-carcinogenic risk, while Pb posed the highest carcinogenic risk. Health risks for humans were greatest from the consumption of mussels. Contaminated shellfish offer the greatest risk for children, subsistence fishers and subsistence shellfish consumers.

Subtidal benthic macroinfaunal assemblages in tropical estuaries: generality amongst highly variable gradients.

South American estuaries are frequently not included in the search for general ecological models and studies dealing with biological assemblages in estuaries frequently do not sample the entire salinity gradient. We sampled three tropical estuaries, two times each, on ten stations distributed along each system. Six replicates were collected in each station for the benthic macroinfauna and sediment samples for grain size and inorganic contaminant analyses. There were finer sediments at the lower than at the upper estuarine portions. There was a decrease in the diversity, at family level, from marine to freshwater and the differences on the structure of the benthic assemblages were mostly spatial. In spite of the many different characteristics of the three estuaries (e.g. catchment size, pollution levels, proximity with the inner continental shelf) several consistent patterns of benthic macrofauna distribution along these systems were still observed. It suggested a general empirical model regarding the distribution of different benthic invertebrates along tropical salinity gradients which can be tested in different estuaries around the world.

A simple and sensitive UFLC-fluorescence method for endocrine disrupters determination in marine waters.

The present study proposes a fast and simple analytical methodology employing C18 SPE cartridges (for preconcentration and clean-up), and a ultra-fast liquid chromatography coupled to fluorescence detector (UFLC-FLD) for determination of the following endocrine disrupters (ED): bisphenol A (BPA), 4-n-nonylphenol (4NNP), 4-n-octylphenol (4NOP), 4-t-octylphenol (4TOP), estriol (E3), estrone (E1), 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) in seawater. The proposed method was developed, optimized and validated. Separation was done by a total running time of 10 min in a Shim-pack XR-ODS C-18 (2.0 mm ID × 50 mm) chromatographic column, mobile phases were acetonitrile/ultra-pure water under gradient programming; eluent flow rate at 0.120 mL min(-1); column temperature set at 60 °C; emission wavelength of 306 nm and excitation wavelength of 280 nm. The method was validated through assessment of the following parameters: linear range, linearity, selectiveness, precision, recovery test, limit of detection (LOD), and limit of quantification (LOQ). Recoveries ranged from 91% (for EE2) to 104% (for 4NNP) and also was found a suitable repeatability (RSD <4.5%) for all considered compounds. LOD and LOQ ranged from 2.0 ng L(-1) (EE2) to 23 ng L(-1) (E1) and 9.3 ng L(-1) (EE2) to 96 ng L(-1) (E1), respectively. The analytical method using SPE UFLC-FLD was applied to seawater samples collected from Todos os Santos Bay (BTS), Brazil to determine the concentration of eight ED.

Detection of environmental impacts of shrimp farming through multiple lines of evidence

In order to evaluate the impact of semi-intensive shrimp farming, comparisons between Control and Impact areas were made based on multiple lines of evidence using an asymmetrical design. Water and sediment samples were collected in four shrimp farms located in Todos os Santos Bay, Bahia, Brazil. Nutrients, trace elements and macrobenthic assemblages were evaluated using uni- and multivariate analyzes. Significant differences were observed between Impact and Control areas for the water column dataset (i.e., ancillary variables, SPM, dissolved nutrients and major and trace elements in SPM), whereas no significant differences were observed for the chemistry of sediments. Macrobenthic assemblages were negatively affected by shrimp farm activities. Impacted sites presented the lowest abundance, richness and different structure of macrofaunal benthic assemblages. Farms clearly produced negative impacts in the Todos os Santos Bay. This conclusion was only possible to be reached through the use of multiple lines of evidence. Chemistry and benthic assemblages data combined produced a better description of the quality and impacts of the evaluated environments. Different conclusions would have been reached if chemistry and ecology results were studied separately vs. together.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3–23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.