Antonio A. Mozeto

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain.

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.

Development of site-specific sediment quality guidelines for North and South Atlantic littoral zones: comparison against national and international sediment quality benchmarks.

We aimed to develop site-specific sediment quality guidelines (SQGs) for two estuarine and port zones in Southeastern Brazil (Santos Estuarine System and Paranaguá Estuarine System) and three in Southern Spain (Ría of Huelva, Bay of Cádiz, and Bay of Algeciras), and compare these values against national and traditionally used international benchmark values. Site-specific SQGs were derived based on sediment physical-chemical, toxicological, and benthic community data integrated through multivariate analysis. This technique allowed the identification of chemicals of concern and the establishment of effects range correlatively to individual concentrations of contaminants for each site of study. The results revealed that sediments from Santos channel, as well as inner portions of the SES, are considered highly polluted (exceeding SQGs-high) by metals, PAHs and PCBs. High pollution by PAHs and some metals was found in São Vicente channel. In PES, sediments from inner portions (proximities of the Ponta do Félix ports terminal and the Port of Paranaguá) are highly polluted by metals and PAHs, including one zone inside the limits of an environmental protection area. In Gulf of Cádiz, SQGs exceedences were found in Ria of Huelva (all analysed metals and PAHs), in the surroundings of the Port of Cádiz (Bay of Cádiz) (metals), and in Bay of Algeciras (Ni and PAHs). The site-specific SQGs derived in this study are more restricted than national SQGs applied in Brazil and Spain, as well as international guidelines. This finding confirms the importance of the development of site-specific SQGs to support the characterisation of sediments and dredged material. The use of the same methodology to derive SQGs in Brazilian and Spanish port zones confirmed the applicability of this technique with an international scope and provided a harmonised methodology for site-specific SQGs derivation.

The fate of trace metals in suspended matter in a mangrove creek during a tidal cycle

The variation of heavy metal content in suspended matter (SM) during tidal cycles in a mangrove creek is described. The stable isotope of carbon was used as a tracer for sources of SM to the system. During tidal cycles three patterns of metal variability were found. The first, represented by Fe, showed an irregular and small variability throughout the cycle; a second, represented by Mn, exhibited a sharp increase in concentration during the rising tide, coincident with the greatest variation of pH and Eh. The third pattern, including Cu, Cd, Pb, Ni, Cr and Zn, showed maximum concentration at the peak of the high tide, coincident with a shift in SM source. The stable isotope of carbon indicated that, during low tides, most of the organic carbon exported originated from mangrove plant detritus, while during the high tides organic carbon imported by the system was almost totally of marine origin. This shift of SM source is the principal parameter controlling metal fluxes through the system. Changes in water pH and Eh, and manganese precipitation, can also serve as a secondary control. Although the results strongly suggest that the metallic load of marine SM is being immobilized by the mangrove environment, mass balance studies are necessary to show whether a net accumulation of metals is actually occurring.

Integrated sediment quality assessment in Paranaguá Estuarine System, Southern Brazil.

Sediment quality from Paranaguá Estuarine System (PES), a highly important port and ecological zone, was evaluated by assessing three lines of evidence: (1) sediment physical-chemical characteristics; (2) sediment toxicity (elutriates, sediment-water interface, and whole sediment); and (3) benthic community structure. Results revealed a gradient of increasing degradation of sediments (i.e. higher concentrations of trace metals, higher toxicity, and impoverishment of benthic community structure) towards inner PES. Data integration by principal component analysis (PCA) showed positive correlation between some contaminants (mainly As, Cr, Ni, and Pb) and toxicity in samples collected from stations located in upper estuary and one station placed away from contamination sources. Benthic community structure seems to be affected by both pollution and natural fine characteristics of the sediments, which reinforces the importance of a weight-of-evidence approach to evaluate sediments of PES.

Use of a La(III)-modified bentonite for effective phosphate removal from aqueous media.

A bentonite from the Northeast Brazilian region was modified with lanthanum (NT-25La) using an ion exchange process. Lanthanum incorporation in the natural clay, as well as the properties of the clay materials, were confirmed by X-ray diffraction, X-ray fluorescence, specific surface area and scanning electron microscopy (SEM/EDX). Phosphate adsorption equilibrium and kinetic tests were performed at different temperatures. The adsorption data have shown that NT-25La reaches equilibrium between modified clay and phosphate solution within 60 min of contact. The phosphate retention at room temperature reached 95%, when initial phosphate concentration in solution was 5 mg L(-1). A kinetic-order variable model provided satisfactory fitting of the kinetic data. Adsorption of phosphate was best described by a Langmuir isotherm, with maximum phosphate sorption capacity of 14.0 mg g(-1). Two distinct adsorption mechanisms were observed that may influence the adsorption processes. The investigation pointed out that the phosphate adsorption occurs via physisorption processes and that the use of NT-25La provides a maximum phosphate sorption capacity higher than many commercial adsorbents.

Calcium nitrate addition to control the internal load of phosphorus from sediments of a tropical eutrophic reservoir: Microcosm experiments

The main objective of this study was to perform laboratory experiments on calcium nitrate addition to sediments of a tropical eutrophic urban reservoir (Ibirité reservoir, SE Brazil) to immobilize the reactive soluble phosphorus (RSP) and to evaluate possible geochemical changes and toxic effects caused by this treatment. Reductions of 75 and 89% in the concentration of RSP were observed in the water column and interstitial water, respectively, after 145 days of nitrate addition. The nitrate application increased the rate of autotrophic denitrification, causing a consumption of 98% of the added nitrate and oxidation of 99% of the acid volatile sulfide. As a consequence, there were increases in the sulfate and iron (II) concentrations in the sediment interstitial water and water column, as well as changes in the copper speciation in the sediments. Toxicity tests initially indicated that the high concentrations of nitrate and nitrite in the sediment interstitial water (up to 2300 mg L(-1) and 260 mg L(-1), respectively) were the major cause of mortality of Ceriodaphnia silvestrii and Chironomus xanthus. However, at the end of the experiment, the sediment toxicity was completely removed and a reduction in the 48 h-EC50 of the water was also observed. Based on these results we can say that calcium nitrate treatment proved to be a valuable tool in remediation of eutrophic aquatic ecosystems leading to conditions that can support a great diversity of organisms after a restoration period.

Harmonised framework for ecological risk assessment of sediments from ports and estuarine zones of North and South Atlantic

This paper presents a harmonised framework of sediment quality assessment and dredging material characterisation for estuaries and port zones of North and South Atlantic. This framework, based on the weight-of-evidence approach, provides a structure and a process for conducting sediment/dredging material assessment that leads to a decision. The main structure consists of “step 1” (examination of available data); “step 2” (chemical characterisation and toxicity assessment); “decision 1” (any chemical level higher than reference values? are sediments toxic?); “step 3” (assessment of benthic community structure); “step 4” (integration of the results); “decision 2” (are sediments toxic or benthic community impaired?); “step 5” (construction of the decision matrix) and “decision 3” (is there environmental risk?). The sequence of assessments may be interrupted when the information obtained is judged to be sufficient for a correct characterisation of the risk posed by the sediments/dredging material. This framework brought novel features compared to other sediment/dredging material risk assessment frameworks: data integration through multivariate analysis allows the identification of which samples are toxic and/or related to impaired benthic communities; it also discriminates the chemicals responsible for negative biological effects; and the framework dispenses the use of a reference area. We demonstrated the successful application of this framework in different port and estuarine zones of the North (Gulf of Cádiz) and South Atlantic (Santos and Paranaguá Estuarine Systems).

BIOLEACHING OF METALS FROM ANAEROBIC SEWAGE SLUDGE: EFFECTS OF TOTAL SOLIDS, LEACHING MICROORGANISMS, AND ENERGY SOURCE

The effects of municipal sewage sludge solids concentration, leaching microorganisms (Thiobacillus thiooxidans or Thiobacillus ferrooxidans) and the addition of energy source (S0 or Fe(II)) on the bioleaching of metals from sewage sludge has been investigated under laboratory conditions using shake flasks. The results show that metal solubilization was better accomplished if additional energy source is supplemented to the microorganisms and that T. thiooxidans furnishes, in general, more adequate conditions for the bioleaching than T. ferrooxidans. At a total solids concentration of 70 gL−1 (originally present in the sludge) pH drop and ORP increase are attenuated, so metal solubilization is negatively affected. It was also demonstrated that if lead (Pb) solubilization is to be achieved, than a special combination of microorganism/energy source must be applied.

Electrical conductivity and emerging contaminant as markers of surface freshwater contamination by wastewater

The use of chemical markers of undoubted anthropogenic sources for surface freshwater contamination by wastewaters was evaluated employing correlations observed between measured physico-chemical parameters as the electrical conductivity and the concentration of different emerging organic compounds. During the period from April/2011 to April/2012 spatial-temporal variations and contamination patterns of two rivers (Piraí and Jundiaí rivers), São Paulo state, Brazil were evaluated. Seven physico-chemical parameters and concentrations of different classes of emerging contaminants were determined in samples collected in seven field campaigns. The high linear correlation coefficients obtained for the compounds diclofenac (r=0.9085), propanolol (r=0.8994), ibuprofen (r=0.8720) and atenolol (r=0.7811) with electrical conductivity, also corroborated by principal component analysis (PCA), point to the potential use of these compounds as markers of investigated surface water contamination by wastewaters. Due to specific inputs, these environmental markers showed very good effectiveness for the identification and differentiation of water body contamination by discharges of treated and untreated urban sewage.

Ecological relevance of Sentinels' biomarker responses: A multi-level approach

In response to the need for more sensitive and rapid indicators of environmental quality, sublethal effects on the lowest levels of biological organization have been investigated. The ecological relevance of these responses assumes a prevailing role to assure effectiveness as indicator of ecological status. This study aimed to investigate the linkages between biomarker responses of caged bivalves and descriptive parameters of macrobenthic community structure. For this purpose a multi-level environmental assessment of marine and estuarine zones was performed in São Paulo coast, Brazil. Multivariate analysis was applied to identify linkages between biological responses and ecological indices, as well as to characterizing the studied stations. Individuals of the marine mussel Perna perna caged along Santos Bay showed signs of oxidative stress, lysosomal membrane destabilization, histological alterations and reduced embryonic development. The estuarine oyster Crassostrea rhizophorae caged along Santos Port Channel showed alterations on biotransformation enzymes and antioxidant system, DNA damage and lysosomal membrane destabilization. The benthic community analysis showed reduced richness and diversity in the same areas of the Santos bay and estuary where biomarker responses were altered. Our results revealed that xenobiotics are inducing physiological stress, which may lead to changes of the benthic community structure and deterioration of the ecological status over time. Integrating biomarker responses and ecological indexes improved certainty that alterations found at community level could be related to xenobiotic as stressors, which was very useful to improve the discriminatory power of the environmental assessment.