Orientador: José Luiz Moraes Vasconcelos / Resumo: Os objetivos foram avaliar o efeito da remoção de bezerros (RB) no desenvolvimento folicular e na indução de ciclicidade e a eficácia do MGA precedendo protocolos de IATF, que utilizam GnRH ou BE, nas taxas de concepção a IATF e gestação. Foram utilizadas 163 vacas paridas em anestro da raça Nelore com 80 ± 29 dias pós-parto e ECC de 3,0 ± 0,29, divididas em 4 grupos: G1: (n=40, controle); G2: (n=42, RB): RB (60 h) 11 dias antes da estação de monta (EM); G3: (n=43, MGA + GnRH): MGA (MGA PREMIX®, 0,5 mg/dia, v.o.) por 10 dias, seguido por RB (60 h), após este período receberam GnRH (CYSTORELIN®, 50 mcg, i.m). Após 6,5 dias, PGF2α (LUTALYSE®, 25 mg, i.m.) que foi seguida por outra RB (54h). Após a RB, todos os animais receberam GnRH e foram inseminados; G4: (n=38, MGA + BE): MGA por 10 dias, seguido por RB (60h), após este período receberam BE (Estrogin , 1,0 mg, i.m.). Após 7 dias, PGF2α que foi seguida por outra RB (54h). Após 24 horas da PGF2α, os animais receberam BE e foram inseminados 30 horas depois. Após a IATF, nos 4 grupos, foi realizado observação de cio e IA (30 d) e por monta natural por mais 32 dias. A ciclicidade, o efeito do MGA e RB no desenvolvimento folicular, as taxas de sincronização, concepção e gestação foram determinados por exames ultra-sonográficos. A variável dias para ficar gestante foi analisada pela curva de sobrevivência, enquanto que as variáveis binomiais e contínuas foram analisadas por regressão logística e pelo GLM do SAS, respectivamente. Foram incluídos no modelo efeito de tratamento, ordem, sexo da cria e suas interações e ECC como co-variável. O MGA foi fornecido, ao G3 e G4, diariamente e os animais ingeriram, em média, 0,99 mg/dia de MGA. O MGA aumentou (P<0,05) o diâmetro do maior folículo (11,2 ± 0,28 vs. 10,3 ± 0,29 mm, respectivamente), que também foi maior (P<0,05) na associação MGA + RB... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objectives of this trial were to evaluate the effects of calf removal (CR) on follicular development and its ability to induce cyclicity and the effects of melengestrol acetate (MGA) preceding TAI protocols, with GnRH or EB on conception and pregnancy rates. Suckled anestrous Nellore cows (n=163) with 80 ± 29 days postpartum and BCS of 3.0 ± 0.29 were assigned into one of four groups: G1: (n=40, control); G2: (n=42, CR): calf removal (60 h) 11 days before the breeding season (BS). G3: (n=43, MGA + GnRH): MGA (MGA PREMIX®, 0.5 mg/day, v.o.) per 10 days, followed by CR (60 h), and GnRH (CYSTORELIN®, 50 mcg, i.m) after CR. Cows received by PGF2α (LUTALYSE®, 25 mg, i.m.) 6.5 days later, and another CR (54h) followed by GnRH and TAI; G4: (n=38, MGA + EB): MGA per 10 days, followed by CR (60h) and injection of EB (Estrogin , 1.0 mg, i.m.) after CR. Cows received PGF2α 7 days later and 24 hours after that, all animals received another EB and were TAI 30 hours later. Calf removal was performed between PGF2α and EB (54 h). After TAI, in all groups, was performed heat detection and AI (30 d) and natural service per more 32 days. Cyclicity status, effect of MGA supplementation and CR on follicular development, synchronization, conception and pregnancy rates were determined by ultrasound. The variable days to pregnancy was analyzed by survival analyses and the binomial and continuous variables were analyzed by logistic regression and GLM of SAS, respectively. The effects of treatment, parity, calf gender and interactions were included in the model, BCS was included as covariable. The MGA was offered to G3 and 4 daily (mixed into the mineral) and the average consumption was 0.99 mg/day. MGA supplementation increased (P<0.05) follicular diameter (11.2 ± 0.28 vs. 10.3 ± 0.29 mm, respectively) Follicular diameter was also increased (P<0.05) when MGA was associated with CR (11.3 ± 0.26 mm)... (Complete abstract click electronic access below) / Mestre

[pt] A água, recurso natural imprescindível, encontra-se cada vez mais escassa e imprópria para o consumo humano. A biossorção é uma tecnologia que utiliza diversos tipos de biomassas, entre elas microrganismos não patogênicos, como Rhodococcus ruber. O objetivo deste trabalho visa a remoção de Co(II) e Ni(II) presentes em soluções aquosas utilizando R. ruber. Estudos microbiológicos, ensaios de biossorção em batelada foram realizados para testar a eficiência da biomassa nos metais pesados Co(II) e Ni(II) através dos parâmetros: pH, concentração de biomassa e concentração do metal. A cinética da reação foi estudada e as isotermas confeccionadas. Espectrometria no infravermelho potencial zeta e microscopia eletrônica foram técnicas utilizadas para conhecimento dos elementos envolvidos no processo biossortivo. Uma remoção de 44 por cento de Co(II) e 36,6 por cento de Ni(II) da solução foi obtida em pH 6 após 180 minutos de contato em solução contendo 3 g.L(-1) de biomassa e 30 mg.L(-1) de metal. A partir da concentração de biomassa de 3 g.L1, observou-se redução na remoção do metal tanto para Co(II) quanto para Ni(II). A isoterma que melhor se ajustou no estudo em questão foi Freundlich para os dois metais. O modelo de pseudo-segunda ordem foi o mais indicado nos estudos cinéticos realizados para os íons Co(II) e Ni(II). Quando avaliados os melhores parâmetros, não foram incrementados grandes graus de remoção utilizando mais uma ou duas fases de biomassa nova na solução. O tratamento da biomassa com NaOH foi o mais eficiente elevando a remoção para 97 por cento de Co(II) e 89,1 por cento de Ni(II). / [en] Water, essential natural resource, is becoming increasingly scarce and unfit for human consumption. The biosorption is a technology that uses various types of biomass, including nonpathogenic microorganism suchs Rhodococcus rubber. This study aims at the removal of Co(II) and Ni(II) present in aqueous solutions using R. rubber. Microbiological studies, batch biosorption test were conducted to test the efficiency of biomass in heavy metals Co(II) and Ni(II) through the pH, biomass concentration and concentration of the metal. The reaction kinetics was studie and the isotherms made. Zeta potencial, infrared spectrometry and electron microscopy techniques were used for knowledge of the elements involved microscopy techniques were used for knowledge of the elements involved in the process biosorption. A 44 per cent removal of Co(II) and 36.6 per cent Ni(II) solution at pH 6 was obtained after 180 minutes of contact in a solution containing 3 g.L(-1) of biomass and 30 mg.L(-1) of metal solution. From the concentration of biomass 3 g.L(-1), there was a reduction in metal removal for both Co(II) and for Ni(II). The isotherm best fit in the current study was Freundlich for the two metals. The model of pseudo-second order was the best in the kinetic studies performed for the Co(II) and Ni(II). When considering the best parameters, therewere increased levels of large removal using one or two phases of new biomass in the solution. Treatment of biomass with NaOH was the most efficient removal rising to 97 per cent of Co(II) and 89.1 per cent Ni(II).

Ett av riksdagens miljömål är att minska övergödande faktorer. En källa till övergödning är kväveutsläpp från avloppsreningsverk. Arvidstorps avloppsreningsverk i Trollhättan väntar en ökad inkommande belastning på grund av befolkningsökning i området samt skarpare krav på utgående halt utsläppt kväve. Detta innebär att planer på att bygga en ny anläggning har satts i verket för att kunna hantera den ökande belastningen. Eventuellt kommer den nya anläggningen inte bli klar innan de nya kraven kommer. Detta gör att reningsverket utreder andra alternativ för att reducera kväve ur avloppsvattnet som kan tas i drift innan den nya anläggningen är klar. Ett alternativ till kväverening är att använda rejektvattenrening eftersom denna avloppsström innehåller höga koncentrationer kväve. Ett annat problem som reningsverket står inför är att kostnaderna för att hantera det avvattnade slammet förväntas öka. Reningsverket utreder därför alternativ för att minska slamvolymen. En biokolsanläggning där biokol tillverkas av det avvattnade slammet skulle kunna vara ett alternativ. Fördelen är att slamvolymen minskar samt att biokol kan användas som vattenrening då det har förmågan att adsorbera ämnen. I detta arbete har två olika tekniker för att rena kväve ur rejektströmmen på Arvidstorps reningsverk studerats. Dessa är dels en beprövad teknik som kallas deammonifikation där kväve renas med bakterier, och dels biokolsadsorption som kvävereningsmetod vilket inte är en lika etablerad reningsteknik på kommunala reningsverk. Deammonifikationsprocessen finns som flera olika tekniker där den som valts för detta arbete är ANITA Mox. ANITA Mox finns som två tillämpningar där den ena är MBBR (Moving Bed Biofilm Reactor) och den andra är IFAS (Integrated Fixed Film Activate Sludge). Målet med detta arbete var att göra en investeingskalkylering för att bedöma hur ekonomiskt försvarbart det är att installera ANITA Mox MBBR eller ANITA Mox IFAS samt uppskatta kvävereningskapaciteten för alternativet med biokolsadsorption. Inga ekonomiska aspekter togs hänsyn till för det senare alternativet.  För beräkningarna byggdes modeller i Excel och två olika experiment utfördes. Pyrolysering av rötrest till biokol och adsorption, samt ett luftningsförsök för att bestämma faktorer som krävs vid beräkning av luftbehov för deammonifikationsprocessen. ANITA Mox MBBR ha de lägsta årskostnaderna, trots att IFAS kan reducera mer kväve och därmed har lägre driftkostnader. IFAS kräver dessutom en mindre volym total sett med reaktor och sedimenteringsbassäng inräknat, men anledningen till den högre kostnaden är de extra instrument och komponenter som krävs till sedimenteringsbassängen med slamretur och den kortare livslängden på dessa komponenter som ger den högre årskostnaden. Biokol som reningsmetod är inte en lämplig metod då det krävs 66 gånger mer rötrest för att producera den mängd biokol som krävs för att rena rejektvattnet. Den rötrest som kommer produceras i en framtida anläggning kan endast reducera 1,5 % av kvävemängden. / One of the environmental goals for the Swedish parliament is to reduce eutrophic factors. A source of eutrophication is nitrogen emissions from waste water treatment plants. Arvidstorp's waste water treatment plant in Trollhättan expects a population increase and sharper requirements for outgoing nitrogen emissions. This means that plans to build a new plant have been put into operation in order to handle the increasing load. The new facility may not be ready before the new requirements come. The waste water treatment plant is therefore investigating other options for reducing nitrogen from the wastewater. An alternative to nitrogen removal is to use reject water purification since this sewage stream contains high concentrations of nitrogen. Another problem facing the waste water treatment plant is that the costs of handling the dewatered sludge is expected to increase. The treatment plant is therefore looking for alternatives to reduce the sludge volume. A biomass pyrolysis plant where biochar is produced by the dewatered sludge could be an alternative since the advantage is that the sludge volume is reduced and that biochar can be used as water purification as it has the ability to adsorb substances. In this work, two different techniques to remove nitrogen from the reject stream at Arvidstorp's treatment plant has been studied. One is a proven technique called deammonification where nitrogen is purified with bacteria, the other one is biochar adsorption as a nitrogen removal process, however not an equally established purification technique on municipal waste water treatment plants. Several different techniques exists as deammonification processes. The one chosen for this work is ANITA Mox. ANITA Mox is available as two implementations where one is MBBR and the other is IFAS. The goals of this work was to make an investment calculation to assess how economically justifiable it is to install either ANITA Mox MBBR or ANITA Mox IFAS and to estimate the nitrogen removal capacity of the alternative with biochar adsorption. No economic aspects were taken into account for the latter option. For the calculations, models were built in Excel and two different experiments were performed. Pyrolysis of digestion residue for biochar production and adsorption, as well as an aeration test to determine the factors required when calculating the air demand for the deammonification process. ANITA Mox MBBR has the lowest annual costs, even though IFAS can reduce more nitrogen and thus have a greater impact on operating costs. IFAS also requires a smaller reactor volume. The reasons for the higher cost are the extra instruments required for the sedimentation basin and the shorter life span of these components which gives the higher annual cost. Biochar as a purification method is not a suitable method as it requires 66 times more sludge to produce the amount of biochar required to purify the reject water. The sludge that will be produced in a future plant can only reduce 1.5% of the nitrogen load.

A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science in Engineering, 2016 / The aim of this research was to reduce heavy metal and sulfate content of acid mine drainage (AMD) through the methods of passive filtration by combining permeable concrete and organic materials. This was to achieve a low cost, yet effective temporary treatment method for rural/poor communities who are affected by AMD. The acids are filtered through layers of alternating pervious concrete and biological composting layers. The concrete layers target removal of heavy metals such as iron, manganese, potassium, and magnesium, etc. through precipitation as well as reduce sulfate content to a small degree along with total dissolved solids. The concrete layers also aid in raising the pH of the AMD to more acceptable levels. The biological layers achieve sulfate remediation through the metabolism of sulfatereducing- bacteria (SRB). This process however required time and the organic layers were thus thicker and less permeable than the concrete layers in order to allow seepage to take place at a reduced rate. A wide variation of composting layers were tested, including cow manure, chicken manure, sawdust, straw, zoo manure, and leaf compost to find an optimum mix of materials which allows for the greatest sulfate reduction through sulfate reducing bacteria in the shortest possible time. Short as well as Long-term testing of rigs was undertaken to establish effectiveness, limitations and lifespan of the filtration systems. AMD from a mine in the Mpumalanga coal fields with exceptionally high sulfate content was used to test effectiveness of the organic materials over a short period of time. With long term testing conducted with a synthetic AMD, due to limited supply from the mine. The short term testing yielded removal of sulfates in the order of 56% when using kraal manure as the biological reagent mixed with sawdust for added organic carbon. The mix percentages by volume were 80%Sawdust to 20%manure and this setup was able to achieve the 56% removal of sulfates within 14 days. The filter also successfully raised the pH to 8 while removing a significant portion of heavy metals. The long term tests showed complete (100%) remediation of sulfates after a period of approximately sixty days. The tests are continuing to determine their finite lifespan and limitations. The results show promise for using the technology as a low cost, temporary measure to protect locally impacted groundwater, especially for isolated and/or rural communities while a permanent long term solution is sought.

A research project submitted to the Faculty of Sciences, University of the Witwatersrand, in partial fulfilment of the requirements for the degree of Master of Science in Environmental Sciences (Coursework and Research Report). Johannesburg, 2016. / Paenibacillus castaneae isolated from acid mine decant (Gauteng, South Africa) was previously shown to tolerate high concentrations of lead (Pb). The ability of the bacterium to tolerate/resist other heavy metals is probable and suggests a role for P. castaneae as a biosorbent for their removal from contaminated wastewaters. The current study aimed at determining whether the bacterium is also resistant to other common metal contaminants specifically, zinc (Zn) and nickel (Ni), found in South African wastewaters for biosorption by P. castaneae. Additionally, the influence of the external factors pH and competing cations on the uptake of these metals by the bacterium was evaluated. Specific rates of metal uptake (Q) were calculated indirectly from quantifying (by spectroscopy) the residual ion concentrations post exposure to 3 mM metal after various treatments. P. castaneae was found to tolerate Zn but showed vulnerability towards Ni. In a binary metal system, the bacterium showed a preferential metal uptake in the order Zn>>Co> Mn with a highest Q of 26 mg Zn/g biosorbent biomass recorded in the presence of Mn at pH 7. On the contrary, in a multimetal complex solution, the order of preference shifted to Co>>Zn with no absorption of Mn at the same pH. The results indicate that both pH and the presence of cations have an effect on the uptake of Zn by P. castaneae that could favour or inhibit its biosorption. The present study confirms the ability of P. castaneae to remove additional metals such as Zn, Mn and Co. These findings further suggest the potential of P. castaneae as a biosorbent for greener clean-up strategies of contaminated water facilities around Gauteng in the way of bioremediation. Keywords: P. castaneae, biosorption, specific metal uptake, zinc, lead, nickel / LG2017

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science in Engineering. Johannesburg, 2016 / The remediation of acid mine drainage (AMD) has received much attention over the years due to the environmental challenges associated with its toxic constituents. Although, the current methods are able to remediate AMD, they also result in the loss of valuable products which could be recovered and the financial benefits used to offset the treatment costs. Therefore, this research focused on the removal of toxic heavy metals as well as the recovery of acid using a low cost adsorbent and acid retardation process, respectively. In the first aspect of the study, three low cost adsorbents namely zeolite, bentonite clay and cassava peel biomass were evaluated for metal uptake. The adsorption efficiencies of zeolite and bentonite, was found to be less than 50% for most metal ions, which was lower compared to the 90% efficiency obtained with cassava peel biomass. Subsequently, cassava peel biomass was chosen for further tests. The metal removal efficiency using the cassava biomass was in the order Co2+> Ni2+> Ca2+> Mn2+> Fe3+> Mg2+. The highest metal removal was attained at 2% adsorbent loading and 30 ˚C solution temperature. Amongst the equilibrium models tested, the experimental data was found to fit well with the Langmuir isotherm model. Column studies using the immobilized cassava waste biomass suggested that the breakthrough curves of most metal ions did not resemble the ideal breakthrough curve, due to the competitive nature of the ions present in the AMD used in this study. However, the experimental data from the column tests was found to correlate well with the Adam-Bohart model. Sulphuric acid recovery from the metal barren solution was evaluated using Dowex MSA-1 ion exchange resins. The results showed that sulphuric acid can be recovered by the resins via the acid retardation process, and could subsequently be upgraded to near market values of up to 70% sulphuric acid using an evaporator. Water of re-usable quality could also be obtained in the acid upgrade process. An economic evaluation of the proposed process also showed that it is possible to obtain revenue from sulphuric acid which could be used to offset some of the operational costs. / M T 2016

Dada a importância estratégica das barragens no Brasil e à disputa de interesses, o descomissionamento dessas estruturas é um assunto inevitável a ser discutido. Um conjunto de casos de descomissionamento de outros países é apresentado e ilustra de maneira abrangente essa questão pouco discutida e ainda não legislada no Brasil. Uma metodologia para avaliação da necessidade de descomissionamento com base no potencial de risco oferecido foi proposta e aplicada aos barramentos constantes do Cadastro de barragens das bacias PCJ, no estado de São Paulo. Apesar de a metodologia não poder ser aplicada em sua total extensão devido à insuficiência de dados do cadastro, é possível perceber quando algumas barragens encontram-se descuidadas, sem nenhum tipo de monitoramento podendo ser elegíveis para escomissionamento. / Due to the importance of dams in Brazil and to different interests, dam decommissioning is an unavoidable issue to be discussed. Some examples of dam removal in some countries are presented to generally elucidate this subject that still hasnt been acknowledged, neither legislated in Brazil. A methodology for evaluation of decommissioning demanding, based on the potential risk offered by dams has been set up and tested over a few dams that are constituent of a data basis of dams of Piracicaba-Capivari-Jundiaí (PCJ) basins, in São Paulo state. Despite the fact that the methodology couldnt be used at its full length due to lack of field data, it has been realized when some dams of the data basis are most despised, recklessly maintained and are contestant for decommissioning.

Este trabalho teve como objetivo principal analisar, em condições de campo, o efeito de lâminas de irrigação e de doses de nitrogênio sobre o comportamento espectral da cultura do feijão, a partir de medidas de reflectância hiperespectral, na faixa de 350 a 1150 nm, e da correlação entre os parâmetros biofísicos e as variáveis agronômicas da cultura, nessas condições. O experimento foi conduzido na área experimental de Agricultura Irrigada da Fazenda Areão, sob a responsabilidade do Departamento de Engenharia Rural da Escola Superior de Agricultura Luiz de Queiroz DER/ESALQ/USP, localizada no município de Piracicaba, SP, de setembro a dezembro de 2007. O delineamento experimental foi em blocos casualizados com parcelas subdivididas, alocando-se, nas parcelas, os tratamentos relacionados aos níveis de irrigação ((179,5; 256,5; 357,5 e 406,2 mm) e nas subparcelas os tratamentos relativos às doses de nitrogênio (0; 80 e 160 kg ha-1), totalizando doze tratamentos em cada bloco. Como os tratamentos foram dispostos em quatro blocos (repetições), o total de parcelas experimentais foi de 48. As medidas radiométricas de campo foram adquiridas por meio do espectrorradiômetro SPECTRON SE-590, em sete datas, durante o ciclo da cultura. Foram coletados, ainda, a altura das plantas, o índice de área foliar, a produtividade de grãos, o número de grãos por vagem e o número de vagens por planta. Os índices espectrais calculados foram o NDVI e o NB_NDVI. Foi aplicada a remoção do contínuo nos espectros de reflectância para analisar a profundidade da banda e a área da banda de absorção, centrada em 665 nm. O fator água influenciou as variáveis biofísicas (IAF, altura da planta, produtividade, número de vagens por planta e número de grãos por vagem), sendo maiores os valores encontrados nas plantas que receberam maiores quantidades de água. O aumento da dose de nitrogênio não influenciou as variações das variáveis biofísicas, devido, possivelmente, ao processo de lixiviação desse nutriente para as camadas abaixo do sistema radicular da cultura. As análises dos índices de vegetação e dos parâmetros da remoção do contínuo (área e profundidade da banda de absorção) mostraram que as lâminas de irrigação afetaram o comportamento espectral do feijão no comprimento de onda de 665 nm, e que esses parâmetros não foram influenciados pelas doses de N. Os índices de vegetação (NDVI e NB_NDVI) e os parâmetros da remoção do contínuo (a profundidade da banda e a área da banda de absorção) foram eficientes na estimativa do IAF, da altura de plantas e da produtividade de grãos. Durante todo o desenvolvimento da cultura, as melhores correlações entre as variáveis biofísicas e as variáveis espectrais foram observadas nos estádios V4 e R6 de acordo com a variável analisada, sendo, portanto, estes os melhores estádios para monitorar espectralmente a cultura. Diante das metodologias utilizadas, as variáveis biofísicas foram mais bem estimadas pelo índice NB_NDVI, nos estádios V4 e R6, quando comparado ao índice NDVI e aos parâmetros da remoção do contínuo (profundidade e área da banda de absorção). / The objective of this research was to analyze the effect of irrigation levels and nitrogen fertilization on the spectral behavior, in the wavelength range of 350 to 1150 nm, of bean crop and the correlation between biophysical parameters and agronomical variables. The experiment was carried on at the Fazenda Areão, located at the University of São Paulo (ESALQ/USP) campus, Piracicaba, São Paulo, Brazil, from September to December, 2007. The experimental design was the randomized blocks, with split plots, with 12 treatments, 4 irrigation levels (179,5; 256,5; 357,5 e 406,2 mm) and 3 nitrogen rates (0; 80 e 160 kg ha-1), and four blocks. The field radiometric data were acquired with the SPECTRON-SE 590 spectroradiometer for seven dates during the crop growing season. Plant height, leaf area index (LAI), grain yield, the pod number per plant and the grain number per pod were also acquired. The spectral indices used were NDVI and NB_NDVI. The continuum removal was applied for the reflectance spectrum, on visible region centered on 665 nm, to analyze the band area and band depth. The irrigation also influenced the biophysical variables, so the largest medium values were observed in the treatments that used the largest irrigation levels. The nitrogen fertilization did not interfere on the biophysical variables, probably due to the leaching process. The vegetation indices and continuum removal analysis showed that irrigation levels affected the spectral behavior of bean crop on 665 nm and this parameters had not been influenced by nitrogen levels. The vegetation indices (NDVI and NB_NDVI) and the continuum removal parameters (band area and band depth) were efficient in the estimate of IAF, plant height and grain yield. During all the crop development, the best correlations between biophysical variables and spectral variables were observed on V4 and R6 stages, according to the variable analized. In face of the methodologies used, the biophysical variables were better estimated by NB_NDVI, on V4 and R6 stages, when compared with NDVI and the continuum removal parameters.

O lodo gerado em processos de galvanoplastia é classificado pela ABNT NBR 10.004/04 como perigoso (classe I). Na literatura encontram-se poucos estudos referentes à recuperação do cromo presente no lodo gerado em sistemas de tratamento de efluentes de indústrias de galvanoplastia. Neste sentido, o presente estudo avaliou a remoção do cromo presente no lodo de galvanoplastia por meio de dois processos, visando avaliar à eficiência técnica e a viabilidade econômica de ambos. O Processo 1 consistiu na remoção do cálcio utilizando o ácido cítrico, seguida de lixiviação ácida. Na etapa de oxidação, variou-se a temperatura em 40ºC, 60ºC e 80ºC e no tempo de 30, 60 e 90 minutos, tendo em vista que a eficiência do processo de oxidação depende da temperatura e tempo. Nesta etapa do processo as concentrações de peroxido de hidrogênio (H2O2) utilizadas foram de 1,50, 3,00 e 4,50 mol.L-1. O Processo 2 realizou a oxidação do cromo sem efetuar as etapas de extração do cálcio e a lixiviação ácida. A oxidação do cromo ocorreu pelo mesmo método apresentado no Processo 1. A caracterização elementar da amostra determinou que o principal elemento constituinte do lodo é o cálcio (20,05% em massa), e que dentre os metais pesados destacam-se o cromo e o níquel (6,52% e 4,33% em massa, respectivamente). A maior eficiência de remoção do cálcio foi obtida na razão mássica de 8,00 (ácido cítrico/hidróxido de cálcio), com 51,76% em massa, seguida pela razão mássica de 5,50 com 36,75% em massa e 2,50 com 24,83% em massa. O melhor resultado de oxidação do cromo no Processo 1 foi obtido com tempo de 30 minutos, temperatura de 60ºC e concentração de peroxido de hidrogênio de 3,00 mol.L-1, com eficiência de 41,09% em massa. No Processo 2, obteve-se a remoção de 37,96% em massa de cromo a temperatura de 80ºC, por uma hora e 3,00 mol.L-1 de peróxido de hidrogênio. Avaliando os custos para remoção do cromo dos dois processos, determinou-se que o Processo 1 foi mais oneroso que o 2, porém ambos não apresentaram viabilidade econômica para aplicação em escala industrial. Nos dois processos efetuou-se a oxidação do cromo presente no lodo de galvanoplastia, permitindo a sua remoção parcial neste resíduo. Com isso obtiveram-se ganhos ambientais, pela diminuição deste elemento no resíduo de galvanoplastia, que na maioria das vezes é disposto em aterros classe I, gerando um passivo ambiental. / The sludge generated in electroplating processes is classified by NBR 10.004/04 as a hazardous material (class I). In the literature, few studies report the recovery of chromium present in the electroplating sludge generated in the industries. In this sense, the present study conducted the removal of chromium in the electroplating sludge through two different processes, aiming to evaluate their efficiency and economic viability. The first process removed calcium through the use of citric acid being performed by varying the ratio of citric acid/calcium hydroxide (2.5, 5.5 and 8.0). Then, were performed the leaching of the samples. According to the literature, the efficiency of the oxidation process varies depending on the reaction temperature, time and concentration of hydrogen peroxide. For this reason, samples were heated to a temperature ranging from 40°C, 60°C and 80°C. Also, were conducted variations in the concentrations of hydrogen peroxide (1.5, 3.0 and 4.5 mol.L-1) and reaction time (30, 60 and 90 minutes). The second Process consisted in the chrome recovery by using the galvanic sludge without removal of the calcium and acid leaching. The chrome oxidation occurred by the same method shown in Process 1. Elemental characterization of the samples determined that the primary sludge constituent was calcium (20.05% by weight), and in terms of heavy metals, the chromium and the nickel (6.52% and 4.33% by mass, respectively). Most of calcium removal efficiency was obtained at a rate of 8 with 51.76% by mass, then the ratio of 5.50 to 36.75% by mass and 2.50 to 24.83% by mass. The best oxidation result of chromium in Process 1 was obtained using a time of 30 minutes, 60°C and hydrogen peroxide concentration of 3 mol.l-1, with 41.09 wt% efficiency. In Process 2 was obtained the removal of 37.96% by mass of chromium temperature of 80°C, for one hour and 3,00 mol.l-1 of hydrogen peroxide. Evaluating the costs for chrome removal of the two processes was determined that the Process 1 was more costly than 2, but both showed no economic feasibility for implementation on an industrial scale. However, in both cases occurred the oxidation of chromium present in the electroplating sludge, allowing its removal from the residue. Thus, environmental gains have been achieved by the reduction of this element in electroplating waste, which mostly is intended for landfill class I, generating an environmental liability.

Atualmente necessitam-se de processos de tratamento de efluentes que sejam mais sustentáveis em longo prazo, e com isso estão sendo desenvolvidos os processos oxidativos avançados (POAs). Estes processos apresentam a capacidade de mineralizar os poluentes, sem apenas transferi-los de fase, como ocorre com muitos métodos de tratamentos convencionais. A mineralização de poluentes, ou seja, a transformação de contaminantes orgânicos em dióxido de carbono, água e ânions inorgânicos, se baseia em reações de degradação que envolvem a geração de espécies altamente oxidantes, tais como o radical hidroxila (&bull;OH). Durante o processo de fabricação, uma determinada quantidade de corante sempre é perdida e com frequência causa problemas ambientais. Os corantes afetam a natureza da água e inibem a penetração da luz solar nos rios reduzindo as suas atividades fotossintéticas. Devido a isso, os efluentes de indústrias que utilizam corantes em seus processos de produção necessitam de tratamentos adequados para a remoção desses contaminantes. Estudou-se então a aplicação da fotocatálise heterogênea (utilizando-se o TiO2 como fotocatalisador) com o objetivo de remover a cor de um efluente sintético contendo corantes de uma indústria de cosméticos (D&C Vermelho 6, Carmim e D&C Laranja 5). Para tal, realizou-se um planejamento experimental 23 em que se encontrou como ponto ótimo de tratamento os valores de 7,0, 0,5 g L-1 e 25&deg;C para pH, concentração de TiO2 e temperatura, respectivamente, obtendo-se uma remoção de cor de 80% com 15 minutos de irradiação. Os experimentos cinéticos mostraram que a fotocatálise heterogênea segue um modelo de ordem 0,5 com constante de velocidade k = (7,2 &plusmn; 1,2) &times; 10-2 min-1 e R2 = 0,997. A fotólise segue um modelo de ordem 1, com constante de velocidade k = (8,9 &plusmn; 2,5) &times; 10-3 min-1 e R2 = 0,977. A diminuição dos valores de DQO, em aproximadamente 80%, demonstra que o efluente foi efetivamente oxidado. O valor encontrado na relação DQO/DBO5,20 para o efluente inicial demonstra que este não é biodegradável, porém após o tratamento, esta relação mostra que o efluente se tornou biodegradável. A remoção de COD, ou seja, a mineralização do efluente foi de aproximadamente 70% com 30 minutos de tratamento. Os valores encontrados de MOC confirmam o já descrito pela DQO, que o efluente foi realmente oxidado pelo tratamento. O efluente bruto apresentou uma leve ecotoxicidade enquanto que após o tratamento não houve ecotoxicidade alguma. Conclui-se com esse estudo que o método da fotocatálise heterogênea removeu a cor do efluente, tornou-o mais biodegradável, removeu sua ecototoxicidade e o mineralizou. / Currently, wastewater treatment processes that are more sustainable in the long term are needed, thus leading to the development of the advanced oxidation processes (AOPs). Those processes have the ability to mineralize pollutants, instead of just transferring them from one phase to another, as it is the case with many conventional treatment methods. The mineralization of pollutants, i.e. the transformation of organic contaminants into carbon dioxide, water and inorganic anions, is based on degradation reactions involving the generation of highly oxidizing species such as hydroxyl radical (&bull;OH). During the manufacturing process, a certain amount of dye is always lost and often causes environmental problems. The dyes affect the nature of water and inhibit the penetration of sunlight into rivers, thus reducing their photosynthetic activity. Because of this, the wastewaters from industries that use dyes in their production processes require appropriate treatment for the removal of these contaminants. Therefore, it was studied the application of heterogeneous photocatalysis (using TiO2 as the photocatalyst) in order to remove the color of a synthetic wastewater containing dyes of the cosmetics industry (D&C Red 6, Carmin, and D&C Orange 5). For that purpose, an experimental design 23 was used and an optimal treatment condition was found: 7.0, 0.5 g L-1 and 25&deg;C for pH, concentration of TiO2 and temperature, respectively, resulting in a color removal of 80% with 15 minutes of irradiation. Kinetic experiments showed that the heterogeneous photocatalysis follows a 0.5 order model, with a constant k of (7.2 &plusmn; 1.2) &times; 10-2 min-1 and R2 of 0.997. Photolysis followed a first order model, with a constant k of (8.9 &plusmn; 2.5) &times; 10-3 min-1 and R2 of 0.977. The COD decrease of approximately 80% shows that the effluent was effectively oxidized. The initial COD/BOD5, 20 ratio demonstrates that the effluent is not biodegradable, but after treatment, that ratio indicated that the effluent became biodegradable. The DOC removal, i.e. the mineralization of the effluent was approximately 70% with 30 minutes of treatment. The MOC confirmed that the effluent was actually oxidized by the treatment. The raw effluent had a slight ecotoxicity while after treatment it became non-toxic. It could be concluded that heterogeneous photocatalysis was able to remove the color of the effluent, to increase its biodegradability, to remove its ecotoxicity and to mineralize it.