Remediation of Eutrophic Aquatic Ecosystems: Evaluation of Phosphorus Adsorption by Sawdust.

A wide range of anthropogenic activities have caused various problems to the aquatic environment, leading to economic, social, and environmental losses. The use of materials for the recovery of water quality is very important due to the water scarcity scenario present in different parts of the world. The use of sawdust as an organic adsorbent for P removal in eutrophic environments attempts to address both water quality preservation and possible application of the organic adsorbent as fertilizer for agricultural practices. This use will result in important contributions to the water and food security. In this work, we performed laboratory experiments to study P adsorption and to evaluate possible adsorption of metals and emerging contaminants by sawdust. The experiments were carried out in 36 microcosms (glass jars), using 50% of the flasks as treatments (containing bags with sawdust) and the rest of the flasks as control (water and sediment without sawdust). For future application of sawdust as a fertilizer it is important to be aware of the presence of possible pathogenic microorganisms, thus the presence of helminth eggs was determined in the sawdust. The results showed the tendency of P adsorption by the biosorbent; maximum adsorption occurred at 214 d (41 µg P g-1 ), after the P desorption occurred. No helminth eggs or emerging contaminants and toxic metal were detected in the sawdust after its use as biosorbent, providing an important subsidy regarding the use of the biosorbent as soil fertilizer. Integr Environ Assess Manag 2019;00:1-12. © 2019 SETAC.

Biosorbent, a promising material for remediation of eutrophic environments: studies in microcosm.

Eutrophication is considered a global environmental problem that causes economic and biodiversity loss. Together with excess phosphorus in some aquatic environments, there is the depletion of phosphate rock deposits, which can directly affect fertilizer production and therefore global food security. Thus, the present work aimed to study a new remediation technique for eutrophic environments that enables the recovery of these environments through phosphorus adsorption in sawdust, creating the possibility to apply the phosphorus-enriched material as an agricultural fertilizer. The study was conducted in 36 microcosm flasks with water and sediment samples from a eutrophic reservoir in Ibirité/MG. The experiment was carried out using 18 control flasks and 18 others as treatment, consisting of water and eutrophic environment sediment and, additionally, two bags, containing 10 g of sawdust in each bag. The phosphorus adsorption on sawdust was more intense after 49 days of immersion in the microcosm, and reductions of 90% in the concentration of reactive soluble phosphorus were observed in the water column of the microcosm treatment at 159 days of the experiment. Based on the results, it can be concluded that, although the phosphorus concentration adsorbed on sawdust (16.2 µg g-1) is considered low, the use of the biosorbent is a particularly promising technique for remediation of eutrophic environments, as well as the possible reuse of the adsorbed phosphorus as a fertilizer in agriculture.

A critical comparison of different approaches to sediment-quality assessments in the Santos Estuarine System in Brazil.

This study focuses on the discussion of different lines of evidence (LoEs) applied to a sediment-quality assessment that considered the following: chemical concentrations of metals; polycyclic aromatic hydrocarbons (PAHs) in estuarine waters, sediments, and oysters (native and caged Crassostrea brasiliana); PAHs in semipermeable membrane devices (SPMDs); simultaneously extracted metals-acid volatile sulfides (SEM-AVS); benthic community assessment (the exploratory benthic index and the relative benthic index); chronic toxicity tests with the sea urchin Lytechinus variegatus; and bioaccumulation models. Significantly contaminated sediments from the Santos Estuarine System and the consequent toxicity of tested organisms were measured. Caged oysters presented bioaccumulation rates ≤2,500% of total PAH content and 200% of metal content when compared with control organisms from an uncontaminated area. SPMD results presented the same bioaccumulation pattern as caged oysters but at lower concentrations. Benthic communities presented some alterations, and there was a predominance of tolerant species in the inner part of the estuary. According to the SEM-AVS approach, metals should be assumed to be nonbioavailable, but experiments with transplanted C. brasiliana showed metal bioaccumulation, particularly in the cases of chromium, copper, mercury, and zinc. The weight-of-evidence approach was applied to compare and harmonize LoEs commonly used in sediment-quality assessments and to then classify estuary environments according to both their potential for having adverse effects on the biota and their possible ecological risks. All of the results of these approaches (except for SEM-AVS) were found to complement each other.

A 3-year study on occurrence of emerging contaminants in an urban stream of São Paulo State of Southeast Brazil.

This manuscript reports a 3-year study on occurrence of pharmaceuticals, hormones, and triclosan in surface waters of a central urban region of São Paulo State of Southeast Brazil (the Monjolinho River in São Carlos). Water samples collected once at every 2 months were pre-concentrated by solid-phase extraction (SPE) and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The most frequently detected compounds in higher concentrations were caffeine, paracetamol, and atenolol (maximum concentrations 129,585, 30,421, and 8199 ng L(-1), respectively), while hormones estrone and 17-ß-estradiol were the least detected, in levels up to 14.8 ng L(-1). There was an increasing trend in concentrations of most of the compounds along the river course, especially downstream of the river where there is discharge of both wastewater treatment plant effluent and raw sewage from a particular region of São Carlos city. Concentrations of contaminants were higher during dry periods as a result of decline in the water levels. Decrease in concentrations near the river mouth occurred to different extents for each compound. It was high for caffeine and atenolol, but was very low for carbamazepine and diclofenac. The present study reports the first data about the occurrence of some major emerging contaminants in the Monjolinho River. Besides its regional significance, this work may assist in composing a dataset for water contamination diagnosis focusing on emerging contaminants, both in the Brazilian as well as in the Global studies related to aquatic ecosystems. Such datasets can be helpful for making future public policies on water quality, since these compounds are not yet legally regulated.

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.

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.

Assessment of organic and inorganic contaminants in sediments of an urban tropical eutrophic reservoir.

Although the Ibirité reservoir (an urban tropical eutrophic reservoir) has been the recipient of the discharge of a large volume of raw urban sewage, the key cause of ecosystem degradation has been historically solely attributed to the discharge of effluents from an oil refinery. This fact motivated an investigation to unravel the compositions of contaminants in the sediments to evaluate their distributions, possible sources, and potential impacts on sediment­water quality. The concentrations of polycyclic aromatic and aliphatic hydrocarbons and of metals and metalloids were, in general, significantly lower than some selected polluted sites used for comparison. Calculated distribution indexes showed that the hydrocarbon sources were petrogenic, pyrogenic, and biogenic. Only a few PAHs exceeded the threshold effects level (TEL) guideline. Industrial activities are the presumed sources of metals and metalloids except for copper, which is from copper sulfate used as algaecide in the reservoir. The bioavailable concentrations of some metal and metalloid exceeded the TEL­PEL guidelines. The acid volatile sulfide concentration was greater than that of the simultaneously extracted metals in the clayey­silty reservoir sediments, whereas the opposite result was observed for the sandy sediments of the tributaries. The sediment interstitial water toxic units were >1 for metals, thus indicating that metals are potentially toxic to the benthos. Considering the data set generated in this study, it can be concluded that the degradation of Ibirité reservoir and its tributaries cannot be solely attributed to the input of hydrocarbons, but predominantly to the discharge of raw urban sewage and effluents from other industrial sources.

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.

Validation of a method for the analysis of PAHs in bulk lake sediments using GC-MS.

This work presents the validation procedures of an analytical method to determine the 16 PAHs from the US EPA's priority pollutants list in sediment samples using ultrasonic extraction coupled to gas chromatography-mass spectrometry. The extraction techniques are altered by the construction of an extraction flask adapted to the ultrasonic bath that greatly reduces losses and increases extraction efficiency of the volatile compounds, especially naphthalene. Cleanup procedures are also altered to change the polarity of the solvent mixture that contributes to reducing the elution of undesirable compounds. The PAH spiked sediment at 100 microg/kg level shows recovery rate of 68% to 108%. A certified reference material has been analyzed for those compounds showing results conforming to certified values. The optimized procedure is applied to sediment samples from different areas across Southeast Brazil and presents the results from the Ibirité Reservoir (MG, Brazil), a eutrophic water body. The total PAH concentration in these sediment samples varies between 103.96 and 180.87 microg/kg (dry weight). As the detected concentrations are relatively low, the acute toxicity detected in sediment and its pore water is not due to these compounds, but to high concentrations of ammonia, copper, and nickel according to TIE procedures.

Dynamics of phosphorus and nitrogen through litter fall and decomposition in a tropical mangrove forest.

Distribution, dynamics and mass budget of phosphorus and nitrogen in a red mangrove forest were studied in the Potengi mangrove forest in northern Brazil (lat. 5 degrees 42' and 5 degrees 53'S, long. 35 degrees 5' and 35 degrees 25'W). Tidal hydrology, net primary productivity, leaf litter decomposition rate and standing stock of leaf litter in a red mangrove forest were measured. The results showed that the main reservoir for total P and total N was the sediment with 309 kg ha(-1) and 4619 kg ha(-1) (77% and 95% of the total P and N content in the mangrove forest), respectively, for the two elements. Total P and total N in Rhizophora mangle trees accounted for 145+/-14 kg ha(-1) and 216+/-23 kg ha(-1) (23% and 5% of the total P and N in the mangrove forest). The estimated average export rates for P and N through leaf litter are 0.5 kg ha(-1)yr(-1) and 1.6 kg ha(-1)yr(-1) respectively. Our measurements support previous results in concluding that mangrove forests efficiently retain P and N.

Application of toxicity identification evaluation to sediment in a highly contaminated water reservoir in southeastern Brazil.

Rasgão Reservoir, located close to the Metropolitan region of São Paulo, Brazil, has been analyzed previously, and its sediment was found to be highly toxic, with high levels of metals and polycyclic aromatic hydrocarbons and a complete absence of benthic life. Polychlorinated biphenyls also were present, as was mutagenic activity, detected with the Salmonella/microsome assay. Because of the extremely complex mixture of contaminants in these sediments, a toxicity identification evaluation was performed on the pore water and elutriate using Ceriodaphnia dubia and Vibrio fischeri. Toxicity characterization, identification, and confirmation procedures were performed in one representative sample of the reservoir, and the results indicated that ammonia was the main cause of the toxicity detected with C. dubia in both sediment pore water and elutriate. Chemical analysis corroborated this observation by revealing un-ionized ammonia concentrations as high as 5.14 mg/L in pore water and 2.06 mg/L in elutriate. These high ammonia levels masked possible toxicity caused by other classes of compounds. The toxicity detected with V. fischeri decreased with the time of sample storage and was related to the organic fraction of the pore water and the elutriate, in which compounds such as benzothiazole and nonylphenol were detected.

Seasonal variations in water quality of an oxbow lake in response to multiple short-time pulses of flooding (Jataí Ecological Station - Mogi-Guaçú 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 m(3).s(-1) to a maximum of 600 m(3).s(-1). Diogo Lake is a shalow 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.

Biogeochemical properties at the Jataí ecological Station Wetlands (Moji-Guaçu River, Säo Paulo, SP)

The relatively large number of scientific publications on natural and constructed wetlands around the world is due to the importance these areas have as critical sites where biogeochemical cycling of elements is extensive on a global scale. The understanding of ecological functions and community structure is highly dependent on the knowledge of those cycles and their interactions. These studies are also relevant because natural or constructed wetlands are sites used worldwide to treat industrial and domestic effluents. This paper reports on a series of studies performed and in progress at the Jataí Ecological Station (Moji-Guaçu river, Luiz Antonio, SP, Brazil) with emphasis on the main biogeochemical properties of aquatic systems found there (lacustrine and riverine). Results obtained during the last 10 years within the scope of the Jataí Project with its various subprojects is just beginning to permit understanding the high complexity of these ecosystems.