Quali-quantitative water behaviour in an intensive swine production catchment in the Atlantic Forest biome, Southern Brazil.

Agriculture is an essential economic activity in Brazil. However, it is also the main source of water quality degradation. Monitoring catchments with agricultural land use is a way to generate information on a scale to identify causes and sources of water quality degradation. This work used monitoring data derived from hydrology and the quality of surface and underground water in an intensive agricultural catchment in the Atlantic Forest biome. The Fortaleza River catchment is located in the western part of Santa Catarina state in southern Brazil and has 62 km2 of drainage area. Hydrological and water quality monitoring was conducted for 7 years at two fluviometric stations, three lysimeters, one meteorological station, and one piezometer. Data on precipitation, temperature, water flow, surface runoff, drainage, and water quality were used. Statistical analyses were also developed. Precipitation between 2013 and 2019 presented a homogeneous distribution in monthly and annual data, with January and July the months with the highest and lowest values, respectively. Statistical difference in the average and Q95 flows was found in upstream and downstream fluviometric sections. In terms of quality, statistical differences were identified for ammonium, nitrate, and potassium concentrations, which had higher concentrations in lysimeter runoff, indicating direct influence of agricultural activity on water quality. Principal component analysis (PCA) indicated that (i) surface water presented a positive relationship in Component 1 for the magnesium-calcium, sulphate-chloride, and acetate-bromide groups and a negative relationship for phosphate-nitrate; (ii) in lysimeters, the positive relationship occurred for Component 2 for the phosphate-chloride and sulphate-nitrate groups and was negative for ammonium-lithium and calcium-potassium-magnesium; and (iii) in piezometer, positive relationships were found for chloride-sodium and phosphate-nitrite pairs, while negative relationships were found for calcium-magnesium.

Biosorption of organic micropollutants onto lignocellulosic-based material.

The occurrence of organic micropollutants such as pharmaceutical drugs and hormones in the environment reflects the inefficiency of traditional wastewater treatment technologies. Biosorption is a promising alternative from a technical-economic point of view, so understanding the mechanisms of adsorption in new biosorbents is vital for application and process optimization. Within this context, this study aims to evaluate the mechanisms of adsorption and removal of synthetic and natural hormones by Pinus elliottii bark biosorbent (PS) compared to commercial granular activated carbon (GAC) through kinetic models, isotherm models, and thermodynamic models. The adsorbents were also characterized by morphology, chemical composition, functional groups, and point of zero charge. Characterization of the adsorbents highlights the heterogeneous and fibrous morphology and broader range of functional groups found for PS. Kinetic adjustments showed high accuracy for pseudo-second-order, Elovich, and intraparticle diffusion models, presenting multilinearity and evidencing multi-stage adsorption. The isotherms for PS followed high-affinity models, predominantly chemisorption, while those for GAC followed the Langmuir model, where physisorption predominates. These mechanisms were confirmed by thermodynamic models, which also indicated a higher dependence on temperature in the adsorption process. In the fortified water removal test, PS showed removal values higher than GAC, highlighting the advantages of this adsorbent.

Biological agents for 2,4-dichlorophenoxyacetic acid herbicide degradation.

Phenoxy herbicides are the most widely used family of herbicides worldwide. The dichlorophenoxyacetic acid (2,4-D) is extensively used as a weed killer on cereal crops and pastures. This herbicide is highly water-soluble, and even after a long period of disuse, considerable amounts of both 2,4-D and its main product of degradation, 2,4 dichlorophenol (2,4-DCP), might be found in nature. Biological decomposition of pesticides is an expressive and effective way for the removal of these compounds from the environment. The role of bacteria as well as the enzymes and genes that regulate the 2,4-D degradation has been widely studied, but the 2,4-D degradation by fungi, especially regarding the ability of white-rot basidiomycetes as agent for its bioconversion, has been not extensively considered. This review discusses the current knowledge about the biochemical mechanisms of 2,4-D biodegradation, focused on the role of white-rot fungi in this process. Finally, the cultivation conditions and medium composition for the growth of 2,4-D-degrading microorganisms are also addressed.

Environmental monitoring model for a drainage basin obtained through spectral analysis of time series.

The quality of results of an environmental monitoring plan is limited to the weakest component, which could be the analytical approach or sampling method. Considering both the possibilities and the fragility that sampling methods offer, this environmental monitoring study focused on the uncertainties caused by the time component. Four time series of nutrient concentration at two sampling points (PB1 and PB2) in the Ribeirão Garcia basin in Blumenau, Brazil, which were significantly correlated to the spatial component, were considered with a 2-hour resolution to develop efficient sampling models. These models were based on the time at which there was the highest tendency toward adverse environmental effects. Fourier spectral analysis was used to evaluated the time series and resulted in two sampling models: (1) the SMCP (sampling model for critical period) that operated with 100% efficiency for registering the highest concentration of nutrients and was valid for 83% of the studied parameters; and (2) the SMGCP (sampling model for global critical period) that operated with 83 and 50% efficiency for PB1 and PB2, respectively.

Copper (Cu) speciation in organic-waste (OW) amended soil: Instability of OW-borne Cu(I) sulfide and role of clay and iron oxide minerals.

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cutotal = 122 mg·kg-1) was amended over 11 years with Cu-rich pig slurry in which Cu was 100 % Cu(I) sulfide. Natural Cu associated with clay and iron oxide minerals persisted in the amended soil, but the exogenous Cu(I) sulfide was unstable. The increase in Cu concentration in the amended soil to 174 mg·kg-1 was accounted for the increase of Cu sorbed to kaolinite and Cu bound to organic matter. These results are important for better understanding the natural occurrence of Cu in soils and for assessing the environmental impacts of organic waste recycling in agricultural fields.

Influencing factors on the removal of pharmaceuticals from water with micro-grain activated carbon.

The removal efficiency of 6 micro-grain AC (µGAC) was examined for 23 selected pharmaceutical compounds, usually found at trace level in municipal wastewater treatment plant (WWTP) effluents. Two different sets of experiments were carried out using distilled water and a real WWTP secondary effluent in order to understand the adsorption mechanisms of pharmaceuticals, including the role of the presence of background organic matter. Physical and chemical properties of µGACs and target pollutants were checked for their potential to predict the pharmaceutical removal. Textural properties of µGACs, and especially the mesopore volume, seemed to play the most important role during the adsorption without background organic matter whereas the chemistry of the µGACs, such as the presence of surface oxygen groups and the point of zero charge, could have more influence in the experiments with WWTP effluent water. Positively charged molecules are better adsorbed due to the influence of the background organic matter and the presence of oxygenated groups in the surface of the µGACs. The UV254 removal correlated well with the pharmaceutical removal and it is confirmed as an indicator to control the performance of pharmaceuticals adsorption with µGACs in tertiary treatment.

Influence of hydroclimatic variations on solute concentration dynamics in nested subtropical catchments with heterogeneous landscapes.

Despite global efforts to monitor water quality in catchments worldwide, tropical and subtropical zones still lack data to study the influence of human activities and climate variations on solute dynamics. In this study, we monitored ten solutes every two weeks for six years (2010-2015) in three nested catchments (2 to30 km2), which contained heterogeneous landscapes composed of forests and agricultural land, and one small neighboring forested catchment (0.4 km2). Data analysis revealed that i) rainfall, discharge and solute concentrations displayed no clear seasonal patterns, unlike many catchments of the temperate zone; ii) solute concentrations in the agricultural area were higher than those in the forested area, but both areas displayed similar temporal patterns due to a common hydroclimatic driver; iii) all four catchments displayed a chemostatic export regime for most of the solutes, similar to catchments of the temperate zone; and iv) a positive correlation was observed between anion concentrations and ENSO (El Niño-Southern Oscillation) index. ENSO appeared to influence both hydroclimatic and anion dynamics in these subtropical catchments.

Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-µm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

Copper and zinc accumulation and fractionation in a clayey Hapludox soil subject to long-term pig slurry application.

Pig slurry (PS) recycling as fertilizer is commonly practiced as an option for minimizing livestock waste. Successive PS applications on the soil can lead to crop toxicity and environmental risk. Despite extensive investigation of macronutrient behavior, the fate of trace metals remains uncertain and only a few long-term field studies have been reported to date. This study was designed to assess the impact of 11-year continuous PS spreading on Cu and Zn accumulation and fractionation in a Brazilian clayey Hapludox soil. Three different PS application rates--50, 100 and 200m3 ha(-1)year(-1)--were monitored at six soil depths in comparison to a non-amended control soil. The modified Geological Survey of Canada sequential extraction protocol was applied. A statistically significant increase in Cu and Zn total concentration (assessed by the sum of fractions) was noted only within the 0-5 cm soil layer for the 50 and 100 m3 ha(-1) year(-1) (PS50 and PS100) treatments, and up to 10-15 cm for the 200 m3 ha(-1)year(-1) (PS200) treatment. The mass balance, determined for the 22 PS amendments over the period, confirmed the overall exogenous Cu and Zn accumulation within the surface layers. More than 70% of the natural heavy metal content was originally in the residual fraction. However, this was the only fraction not influenced by the PS amendments. After PS input, the exogenous Cu was mainly detected in the fraction bound to organic matter (66.4%) within the PS200 0-5 cm soil layer. Exogenous Zn was mainly distributed between the adsorbed fraction (36.7%) and the organic matter fraction (32.0%) within the PS200 0-5 cm layer.

Simulating transport of nitrogen and phosphorus in a Cambisol after natural and simulated intense rainfall.

Intense rainfall adversely affects agricultural areas, causing transport of pollutants. Physically-based hydrological models to simulate flows of water and chemical substances can be used to help decision-makers adopt measures which reduce such problems. The purpose of this paper is to evaluate the performance of SWAP and ANIMO models for simulating transport of water, nitrate and phosphorus nutrients, during intense rainfall events generated by a simulator, and during natural rainfall, on a volumetric drainage lysimeter. The models were calibrated and verified using daily time series and simulated rainfall measured at 10-minute intervals. For daily time-intervals, the Nash-Sutcliffe coefficient was 0.865 for the calibration period and 0.805 for verification. Under simulated rainfall, these coefficients were greater than 0.56. The pattern of both nitrate and phosphate concentrations in daily drainage flow under simulated rainfall was acceptably reproduced by the ANIMO model. In the simulated rainfall, loads of nitrate transported in surface runoff varied between 0.08 and 8.46 kg ha(-1), and in drainage form the lysimeter, between 2.44 and 112.57 kg ha(-1). In the case of phosphate, the loads transported in surface runoff varied between 0.002 and 0.504 kg ha(-1), and in drainage, between 0.005 and 1.107 kg ha(-1). The use of the two models SWAP and ANIMO shows the magnitudes of nitrogen and phosphorus fluxes transported by natural and simulated intense rainfall in an agricultural area with different soil management procedures, as required by decision makers.

Tratabilidade do lodo biológico têxtil e produção de biogás em reator UASB em diferentes temperaturas / Textile biological sludge treatability and biogas production in UASB reactor under different temperatures

RESUMO Neste trabalho avaliou-se o comportamento de um reator UASB em escala laboratorial (16 L) no tratamento de lodo biológico têxtil com produção de biogás, operando em diferentes temperaturas, 35 (mesofílica), 45 e 55ºC (termofílica), com tempo de detenção hidráulica (TDH) constante de 24 h. O reator UASB apresentou-se apto a tratar o lodo têxtil, sendo influenciado positivamente pelo incremento da temperatura, mostrando maiores remoções nas temperaturas termofílicas e com altas taxas de remoção de todos os parâmetros físico-químicos monitorados: demanda química de oxigênio (DQO) (97% em 45 e 55ºC), demanda bioquímica de oxigênio (DBO) (95% em 45ºC e 94% em 55ºC), fósforo total (P-total) (95% a 45 e 55ºC) e nitrogênio total (N-total) (94% a 45 e 55ºC). Quanto à produção de biogás e à concentração de metano, os maiores valores foram observados a 45ºC. Com base nos resultados alcançados, confirmam-se a tratabilidade do lodo têxtil e a produção de biogás em UASB, com melhor performance a 45ºC.

ABSTRACT The aim of this work was to evaluate the behavior of a laboratory-scale UASB reactor (16 L) in the treatment of textile biological sludge with biogas production, operating at different temperatures - 35 (mesophilic), 45 and 55ºC (thermophilic) -, with constant hydraulic retention time of 24 h. The UASB reactor was able to treat the textile sludge, being positively influenced by increasing temperature, with greater removals in thermophilic temperatures and high removal rates of all monitored physical and chemical parameters: chemical oxygen demand (COD) (97% at 45 and 55ºC), biochemical oxygen demand (BOD) (95% at 45ºC and 94% at 55ºC), total phosphorus (P-total) (95% at 45 and 55ºC) and total nitrogen (N-total) (94% at 45 and 55ºC). As for biogas production and methane concentration, the highest values were observed at 45ºC. Based on the results, textile sludge treatability and biogas production in UASB are confirmed, with best performance at 45ºC.

Eficiencia do melaco como fonte de carbono na remocao de nitrito em lixiviados de aterros sanitarios / Molasses efficiency as carbon source in nitrite removal from landfill leachates

Neste trabalho simulou-se a desnitrificação via nitrito em lixiviado de aterro sanitário, operando-se em escala laboratorial através de um reator em batelada sequencial (RBS) adicionando-se melaço de cana como fonte externa alternativa de carbono. As razões DBOlixiviado+melaço/N-NOx estudadas foram 0,37; 4; 12 e 14 com tempo de reação anóxica de 4,33 h (DBO/N-NOx=0,37; 4 e 14) e 22 h (DBO/N-NOx=12). A taxa específica de desnitritação foi de 0,07 kg nitrito.kg-1 sólidos suspensos voláteis (SSV)*dia após 4,33 h de reação anóxica nos ensaios sem adição de melaço de cana e 0,19 e 0,12 kg nitrito.kg-1 SSV*dia nos ensaios realizados com adição de melaço de cana, fornecendo uma razão DBO/N-NOx de 4 e 14, respectivamente. Ampliando-se o tempo de reação anóxica para 22 h e realizando os ensaios sob razão DBO/N-NOx de 12, a taxa específica de desnitritação foi aumentada para 0,55 kg nitrito.kg-1 SSV*dia.

In this work, the denitrification was simulated via nitrite at landfill leachate, operating at laboratory scale through a sequencing batch reactor (SBR) adding cane molasses as an alternative external source of carbon. The reasons BODlandfill leachate+molasses / N-NOx studied were 0.37, 4, 12 and 14 with aNOxic reaction time of 4.33 h (BOD/N-NOx=0.37, 4 and 14) and 22 h (BOD/N -NOx=12). The specific rate of denitritation was 0.07 kg nitrite.kg volatile suspended solids (VSS)* day after 4.33 h of aNOxic reaction in tests without the addition of cane molasses and 0.19 and 0.12 kg nitrite.kg-1 VSS*day in the tests with the addition of cane molasses, providing a ratio BOD/N-NOx 4 and 14, respectively. Widening the aNOxic reaction time to 22 h by performing tests on ratio BOD/N-NOx 12, the specific rate of denitritation was increased to 0.55 kg nitrite.kg-1 VSS*day.

Determinação do coeficiente de reaeração em rios através do uso do traçador gasoso GLP / Determination of stream reaeration coefficients by use of GLP gas tracer

A oxigenação da água constitui-se em importante fator no desenvolvimento do fenômeno de autodepuração de rios. A reposição do oxigênio dissolvido pode ser representada pelo coeficiente de reaeração (K2). Neste trabalho foi testado o uso do GLP como fonte do traçador gás propano em ensaios de reaeração. Foram executados 15 ensaios em trechos de rios com características hidrodinâmicas distintas. Os experimentos mostraram que a utilização do GLP como fonte do traçador gasoso é viável, tanto do ponto de vista analítico, quanto do ponto de vista econômico. Do ponto de vista analítico, os resultados foram equiparáveis e até superiores à técnica tradicional de traçador gasoso. Do ponto de vista econômico, houve redução do custo para a realização de cada ensaio.

The water oxygenation constitutes an important factor in the development of self-purification phenomenon in rivers. The replenishment of dissolved oxygen in water can be represented by the reaeration coefficient (K2). This work was used propane contained in the GLP as tracer in reaeration tests. The tests showed that the use of LPG is feasible, both from analytical point of view, as of the economic. From an analytical standpoint, the results were comparable and even superior to the traditional technique of tracer gas. From an economic standpoint, the cost to perform each test has been reduced.

Relações entre diversidade íctia e fatores hidrodinâmicos de um riacho na bacia do rio Uruguai / Relationship between ichthyofaunal diversity and hydrodynamic factors in a stream of Uruguay river basin

Physical, chemical and environmental factors in watercourses can exert influence on the structure and diversity of species of aquatic biota. Among the physical factors there are hydrodynamic conditions. Disposal variations result into complex dynamics of fish populations and communities. This study aims at assessing the correlation between hydrodynamic variables in the Fortaleza stream, affluent of Uruguay River, and species diversity. The methodology included the collection of hydrodynamic (average depth of the water column, average water flow speed and discharged water in the pluvial metric section) and biological (fish collection in the areas of influence on pluvial metric sections) data. Shannon diversity indices, equitability and the similarity index were calculated with biological data. It has been collected a sample with 527 fishes. There were 25 species, being 4 exotic ones and 4 species not-yet-classified. Such species included 4 orders, 7 families and 13 genera classified. The Shannon index ranged from 1.43 to 2.68 nats/individual. The equitability index was always above 0.8 indicating that individuals are well distributed among different species. The similarity index of Jaccard ranged between 20 and 80%. The lowest figures were obtained from the sample area located near the source. The correlations between the Shannon index and hydrodynamic features resulted in R² coefficients ranging between 0.59 and 0.83. These results show that diversity of species is influenced by the hydrodynamic characteristics. Nevertheless, either depth of water column or discharge average speed is not significant enough to explain the spatial variability of the diversity of species.

Fatores físicos, químicos e ambientais em um curso de água podem influenciar a estrutura e a diversidade das espécies da biota aquática. Entre os fatores físicos têm-se as condições hidrodinâmicas. Variações do escoamento resultam em dinâmicas complexas das populações e comunidades de peixes. Este trabalho tem por objetivo avaliar as correlações entre as variáveis hidrodinâmicas no Arroio Fortaleza, afluente do rio Uruguai, e a diversidade das espécies. A metodologia compreendeu a coleta de dados hidrodinâmicos (profundidade média da coluna de água, velocidade média do escoamento e vazão escoada na seção fluviométrica) e biológicos (coleta de peixes nas áreas de influência das seções fluviométricas). Com os dados biológicos foram calculados os seguintes índices: o de diversidade de Shannon, o de equitabilidade e o de similaridade. Coletaram-se 527 exemplares, de 25 espécies, dentre elas 4 exóticas e 4 ainda não classificadas. Essas 25 espécies estão classificadas em 4 ordens, 7 famílias e 13 gêneros. O índice de Shannon variou entre 1,43 e 2,68 nats/indivíduo. O índice de equitabilidade foi sempre superior a 0,8, indicando que os indivíduos estão bem distribuídos entre as diferentes espécies. O índice de similaridade de Jaccard variou entre 20 e 80%. Os menores valores foram obtidos para a área amostral situada próximo da nascente. As correlações entre o índice de Shannon e as características hidrodinâmicas resultaram em coeficientes R² variando entre 0,59 e 0,83. Estes resultados evidenciam que a diversidade das espécies é influenciada pelas características hidrodinâmicas. No entanto, a profundidade da coluna de água ou a velocidade média do escoamento não são suficientemente significativas para explicar a variabilidade espacial da diversidade das espécies isoladamente.

Classificação dos pesticidas usados na bacia hidrográfica do Itajaí (SC) quanto ao risco de degradação dos recursos hídricos / Classification of the pesticides used on the itajai river hydrographical basin (SC) Brazil for the risk of hidric resources degradation

Os limites de detecção (LD) e de quantificação (LQ) de métodos para análise de resíduos de pesticidas em determinada matriz são essenciais para o estabelecimento da capacidade analítica na determinação qualitativa e quantitativa de traços de substâncias químicas embutidos na mesma. A determinação desses limites em uma matriz exige a condução de ensaios experimentais com a proposição dos LQ e LD em níveis de concentrações que atinjam a sensibilidade a que o método se propõe. Em análise de resíduos de pesticidas em alimentos, os Limites Máximos de Resíduos (LMR) permitidos para cada tipo de cultura estabelecidos pela ANVISA (mg/kg de peso da matriz) podem constituir parâmetro inicial. Neste estudo, apresentou-se metodologia para a determinação desses limites em maçã para os seguintes pesticidas organohalogenados: clorotalonil, captana, dicofol, endossulfam I, endossulfan II, endossulfan sulfato e vinclozolina. Os resultados de LD e LQ do método ensaiado para a exatidão (RM porcentagem =64 por cento a 127 por cento) e precisão (CVporcentagem=2,11 por cento a 12,55 por cento) enquadraram-se nos valores indicados na literatura para considerar tais parãmetros como validados. Além disso, a metodologia empregada demonstrou capacidade para atinjir valores de LQ e LD em concentrações abaixo dos recomendados pela legislação com a utilização de técnicas analíticas alternativas 9CG/ECG/ECD) para a confirmação dos resultados.