Ecotoxicological risks of calcium nitrate exposure to freshwater tropical organisms: Laboratory and field experiments.

This study aimed to analyze laboratory and field data to assess the ecotoxicological risks of calcium nitrate exposure to freshwater tropical biota. Short-term laboratorial tests resulted in estimated EC50 values of 76.72 (67.32-86.12)mg N-NO3₋ L(-1) for C. silvestrii and 296.46 (277.16-315.76) mg N-NO3₋ L(-1) for C. xanthus. Long-term laboratorial tests generated IC25 values of 5.05 (4.35-5.75) and 28.73 (26.30-31.15) mg N-NO3₋ L(-1) for C. silvestrii and C. xanthus, respectively. The results from in situ mesocosm experiments performed in the Ibirité reservoir (a tropical eutrophic urban water body located in SE Brazil) indicated that C. silvestrii and C. xanthus were not under severe deleterious acute impact due to the treatment because the higher nitrate concentrations determined were 5.2 mg N-NO3₋ L(-1) (t=24 h; sediment-water interface) and 17.5 mg N-NO3₋ L(-1) (t=600 h; interstitial water). However, an abrupt decrease in the densities of Cyanophyceae members and other benthic taxa was observed. In summary, the present work contributes greatly to the toxicity data linked to two taxonomically distinct organisms that have never been screened for calcium nitrate sensitivity. Furthermore, considering the problem of the management and restoration of eutrophic environments, our study reports a comprehensive field assessment that allows the elucidation of the possible toxic impacts caused by the addition of calcium nitrate (a remediation technique) on aquatic and benthic organisms as well as the implications on the aquatic ecosystem as a whole, which may greatly allow expanding the current knowledgebase on the topic.

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).

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.

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 port's 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.

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 g L-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.

Estimates of benthic fluxes of nutrients across the sediment-water interface (Guarapiranga reservoir, São Paulo, Brazil).

Concentration profiles of nutrients (dissolved organic carbon, nitrate, nitrite, ammonium and soluble reactive phosphorus) were determined in pore waters from sediment from the Guarapiranga reservoir (São Paulo, Brazil). Redox potential and acid volatile sulfide measurements on bulk sediment samples were determined in the field and laboratory, respectively. The sediment redox potential ranged from -170 to -220 mV at 0-1 cm and increased to somewhat higher values at 20 cm. The acid volatile sulfide (AVS) profile had a bimodal pattern with concentration peaks at 3 cm (27-55 mg kg(-1)) and 14 cm (70-110 mg kg(-1)). Dissolved organic carbon (DOC) concentrations increased from the surface (4.7-5.6 mg l(-1)) to 20 cm (values up to 12 mg l(-1)). The concentration of ammonium increased significantly with depth, with maximum concentrations occurring at 15 cm; nitrate-nitrite concentrations only increased appreciably at 10 cm. The SRP profiles increased in concentration from the surface to approximately 10-cm depth, with a maximum value of 1200 microg H2PO4- l(-1). Benthic fluxes from the sediment into the pore water ranged from 278 to 339 mg cm(-2) year(-1) for ammonium ions and from 8 to 18 mg cm(-2) year(-1) for SRP. These upward diffusive fluxes correspond to 47-70% and to 10-24% of the total deposition of N and P measured in the reservoir, respectively. The burial rates for N and P in these sediments are 30-54% and 76-89%, respectively.

Seasonal variations in water quality of an oxbow lake in response to multiple short-time pulses of flooding (Jataí Ecological Station--Mogi-Guaçu River, Luiz Antonio, SP-Brazil).

Mogi-Guaçu River is a six-order floodplain river in the upper Paraná River Basin, Southern Brazil. Its yearly discharge varies from a minimum of 100 m3.s-1 to a maximum of 600 m3.s-1. Diogo Lake is a shallow lake located at its floodplain within the Jataí Ecological Station (Luiz Antonio, São Paulo State) and is connected throughout the year to the river through a narrow and shallow channel. The main finding of this study is that the river hidrology controls the annual variations in lake hydrochemistry through a series of hydraulic effects related to oscillations in river discharge. Lake water quality is a resultant of differential contribution from local and regional watersheds. During the low water period, lake water quality is determined by inputs from Cafundó Creek, which drains the local watershed into the lake. Raising the river level during the rain season results in the damming of lake and culminates with the entrance of river waters into the plain. The geochemistry of waters in this system is determined by weathering of sandstones with basalt intrusions. Waters are acidic (river pH = 6.00 to 7.02 and stream-lake pH = 5.15 to 6.7) and dominant cations are Na+ and K+. Major anions are almost exclusively represented by bicarbonate and an unknown concentration of organic acid anions. The overall ionic load of these soft waters in the system is therefore very low.