FROM OLIGO TO EUTROPHIC INLAND WATERS: ADVANCEMENTS AND CHALLENGES FOR BIO-OPTICAL MODELING Presidente Prudente 2017 UNIVERSIDADE ESTADUAL PAULISTA “JÚLIO DE MESQUITA FILHO” CAMPUS DE PRESIDENTE PRUDENTE FACULDADE DE CIÊNCIAS E TECNOLOGIA Programa de Pós-Graduação em Ciências Cartográficas THANAN WALESZA PEQUENO RODRIGUES FROM OLIGO TO EUTROPHIC INLAND WATERS: ADVANCEMENTS AND CHALLENGES FOR BIO-OPTICAL MODELING Presidente Prudente 2017 Thesis presented to the Department of Cartography of the Faculty of Science and Technology of São Paulo State University as part of the requirements for obtaining the PhD degree in Cartographic Sciences. Advisor: Prof. Dr. Nilton Nobuhiro Imai Co-Advisor: Prof. Dr. Enner Herenio de Alcântara FICHA CATALOGRÁFICA Rodrigues, Thanan Walesza Pequeno. R617f From oligo to eutrophic inland waters: advancements and challenges for bio-optical modeling / Thanan Walesza Pequeno Rodrigues. - Presidente Prudente : [s.n.], 2017 145 f. : il. Orientador: Nilton Nobuhiro Imai Coorientador: Enner Herenio de Alcântara Tese (doutorado) - Universidade Estadual Paulista, Faculdade de Ciências e Tecnologia Inclui bibliografia 1. Modelagem bio-óptica. 2. Águas interiores. 3. Sensoriamento remoto da água. 4. Sistema de reservatórios em cascata. I. Rodrigues, Thanan Walesza Pequeno. II. Imai, Nilton Nobuhiro. III. Alcântara, Enner Herenio de. IV. Universidade Estadual Paulista. Faculdade de Ciências e Tecnologia. V. Título. To God. To my beloved parents Waldete and Salatiel To my beloved husband Ulisses To my dear sisters and brother Suzan, Rejane and Walesson. AGRADECIMENTOS Agradeço antes de tudo à Deus por ter me concedido grandes oportunidades e me dado forças para sempre prosseguir. A caminhada durante o doutorado foi árdua e sem ele nada teria valido a pena. Nessa jornada contei com ajuda e colaboração de muitas pessoas e a elas eu expresso meus sinceros agradecimentos em especial: A meus pais que tanto amo Waldete e Salatiel por me fazerem chegar onde estou hoje sem medirem esforços, agradeço a dedicação incondicional, amor e ensinamentos passados ao longo de toda minha vida. Aos meus irmãos Waleska, Walesson e Rejane pelo companheirismo, amizade e amor. A meu marido e amigo Ulisses que sempre esteve presente na minha caminhada acadêmica e profissional me incentivando e apoiando as decisões mais difíceis. Aos meus tios e primos queridos: Cris, Walmir, Waldemir, Heloisa, Amandinha, Adonis e Ágatha. Ao meu orientador Dr. Nilton Imai pelas contribuições e por ter possibilitado meu ingresso no Programa de Pós-Graduação da Unesp. Ao meu co-orientador Dr. Enner Alcântara, profissional que realmente se dedica à pesquisa e ciência, que me incentivou desde o princípio a escrever e acreditar no meu potencial como pesquisadora. Ao Dr. Deepak Mishra da Universidade da Geórgia, Estados Unidos, pelo exemplo de pesquisador, e que me ajudou, durante o período sanduíche, com discussões sobre a tese e artigos e que me inseriu no seu grupo de pesquisa em Athens. Agradeço ainda o Departamento de Geografia da UGA por ter concedido ajuda de custo para participar de um evento na cidade de São Francisco. Agradeço a todos os meus colegas e grandes parceiros do grupo de pesquisa em Sensoriamento Remoto da água, em especial: Fernanda, Luiz, Nariane, Alisson, Bruno, Stela, Carol Ambrósio e todos aqueles que direta ou indiretamente fizeram com que as análises e campos ocorressem. Agradeço ainda a todos os meus colegas de Pós-Graduação que me ajudaram a sobreviver no primeiro ano de doutorado seja em sala de aula ou jogando vôlei de areia ou ainda futebol. Agradeço ao Dr. Cláudio Clemente do INPE pelos equipamentos emprestados nos primeiros campos. Agradeço ainda o Renato e Daniel pela ajuda nos campos e nas análises laboratoriais. Ao Dr. Edivaldo Velini e técnicos da Unesp Botucatu, por nos deixar utilizar os equipamentos para análises laboratoriais. A todos os professores do PPGCC por todo ensinamento e discussões, em especial: as Professoras Lourdes, Ivana e Vilma pelas contribuições na tese e em artigos escritos com colaboração. Aos meus colegas Ike e Kumar por ter tornado minha vida mais fácil nos EUA, e por terem me ajudado com discussões relacionados aos artigos. Agradeço ainda a Dipanwita e Shuvo pela gentileza e por terem me apresentado a cultura indiana. Agradeço também ao Benjamin pelas discussões relacionadas a programação ou mesmo com o idioma inglês. Agradeço a CAPES pela concessão da bolsa de doutorado (Processo n° 1193768), ao CNPq pela concessão da bolsa sanduíche (Processo nº 200152/2015-7 - SWE) e por financiar projetos (Processos nº 472131/2012-5 e 400881/2013-6) e à FAPESP pelos projetos (Processos n° 2012/19821-1 e 2015/21586-9). Por fim agradeço à Unesp e o PPGCC pela infraestrutura e suporte para estudo. Agradeço ainda os funcionários da Unesp, em especial a Cinthia, André e Ivonete da Secretaria da Pós-Graduação. Obrigada a todos! “We must have perseverance and above all confidence in ourselves. We must believe that we are gifted for something and that this thing must be attained.” (Marie Curie) RESUMO O presente trabalho teve como objetivo realizar um levantamento detalhado das características bio-ópticas nos reservatórios de Barra Bonita (BB) e Nova Avanhandava (Nav) com o intuito de avaliar o desempenho de uma única abordagem voltada para a estimativa das propriedades ópticas inerentes (POIs), assim como, a concentração de totais sólidos suspensos (TSS). A investigação foi realizada utilizando dados coletados no campo entre 2014 e 2016, incluindo, as POIs, componentes opticamente significativos (COSs) e reflectância de sensoriamento remoto (𝑅𝑟𝑠). Os dados apresentados dos COSs confirmaram que BB é um ambiente mais túrbido que Nav por apresentar maior produção fitoplanctônica em função do recebimento de altas cargas de nutrientes provenientes da bacia de drenagem. Por outro lado, Nav é um ambiente mais transparente e com maior influência de material inorgânico, o que favorece o surgimento de macrófitas submersas. A concentração de clorofila-a (Chl-a) em BB alcançou máximo de 797.8 µg l-1 em outubro/2014, enquanto Nav apresentou máximo de 38.6 µg l-1 em maio/2016. A variabilidade nos COS esteve altamente vinculada a frequência de chuvas, sendo que no ano de 2014, ocorreu um evento extremo de seca alterando as características biogeoquímicas dos ambientes. BB reagiu de forma mais abrupta que Nav por apresentar um sistema de operação do tipo acumulação e por estar mais próxima das regiões potencialmente poluidoras, diferente de Nav que apresenta um sistema fio-d’água em que não há acumulação e sim fluxo constante da água. Além disso, no âmbito óptico, a absorção em Nav apresentou maior influência do particulado não-algal (NAP) enquanto que em BB, a absorção foi dominada por fitoplâncton. Com base nesses resultados pode-se concluir que os dois ambientes apresentam não só diferenças na qualidade da água, mas também nas propriedades ópticas, o que leva a afirmação de que um modelo único baseado nos dois ambientes pode não ter um bom resultado quando se pretende utilizar uma abordagem empírica. Um algoritmo quase- analítico (QAA) parametrizado para as condições de Nav (QAAOMR) apresentou resultados significativos com erros (erro médio percentual absoluto – MAPE) inferiores a 17% para o coeficiente de absorção total (𝑎𝑡), 19% para o coeficiente de absorção orgânico detrital (𝑎𝐶𝐷𝑀) e 47% para o coeficiente de absorção do fitoplâncton (𝑎𝜙). O respectivo modelo foi utilizado para verificar seu desempenho em um ambiente eutrofizado como BB e a versão parametrizada por Watanabe et al. (2016) e denominada QAABBHR foi aplicada aos dados de Nav. Como resultado, observamos que as duas versões foram adequadas para estimar 𝑎𝑡 com erros inferiores a 40%, no entanto, existe ainda a necessidade de melhorar as etapas para estimativa de 𝑎𝐶𝐷𝑀 e 𝑎𝜙. No caso de se aplicar um modelo empírico de única abordagem para estimar concentração de TSS para ambos os reservatórios, observamos que essa abordagem não apresentou resultados satisfatórios, portanto, modelos específicos baseados na banda do vermelho do MODIS foram utilizados para mapear TSS em cada um dos reservatórios. Pode- se concluir então, que o conhecimento acerca das propriedades ópticas da água se mostrou determinante para a modelagem bio-óptica, principalmente no que diz respeito aos ambientes altamente contrastantes como BB e Nav. Palavras-chave: modelagem bio-óptica, águas interiores, sensoriamento remoto da água, sistema de reservatórios em cascata ABSTRACT The objective of the present work was to perform a detailed survey of the bio-optical characteristics of the reservoirs of Barra Bonita (BB) and Nova Avanhandava (Nav) in order to evaluate the performance of a single approach aimed at estimating the inherent optical properties (IOPs), as well as the concentration of total suspended solids (TSS). The research was carried out using data collected in the field between 2014 and 2016, including the IOPs, optically significant components (OSCs) and remote sensing reflectance (𝑅𝑟𝑠). The data presented from the OSCs confirmed that BB is more turbid than Nav because it presents higher phytoplankton production due to the input of high nutrient loads from the drainage basin. On the other hand, Nav is more transparent with greater influence of inorganic matter, which favors the appearance of submerged macrophytes. The concentration of chlorophyll-a (Chl-a) in BB reached a maximum of 797.8 μg l-1 in October/2014, while Nav presented a maximum of 38.6 μg l-1 in May/2016. The variability in the COS was highly related to the frequency of rainfall, in the year 2014, an extreme drought event occurred, altering the biogeochemical characteristics. BB reacted more abruptly than Nav because it presented an accumulation type operation system and because it is closer to the potentially polluting region. Nav presents a water system in which there is no accumulation but constant flow of water. In addition, in the optical context, the absorption in Nav presented greater influence of the non-algal particulate (NAP) while in BB, the absorption was dominated by phytoplankton. Based on these results, it can be concluded that the two environments present not only differences in water quality but also in optical properties, which leads to the assertion that a single model based on the two environments may not have a good result when it is intended to use empirical approach. A quasi-analytical algorithm (QAA) parameterized for Nav conditions (QAAOMR) presented significant results with errors (mean absolute percentage error - MAPE) lower than 17% for the total absorption coefficient (𝑎𝑡), 19% for the carbon detrital matter absorption coefficient (𝑎𝐶𝐷𝑀) and 47% for the absorption coefficient of phytoplankton (𝑎𝜙). The respective model was used to verify its performance in a eutrophic environment such as BB and the version parameterized by Watanabe et al. (2016) and named QAABBHR was applied to the Nav data. Thus, we note that the two versions were suitable for estimating 𝑎𝑡 with errors (MAPE) less than 40%, however, improvements must be carried out for estimating 𝑎𝐶𝐷𝑀 and 𝑎𝜙. In the case of applying a single empirical model to estimate TSS concentration for both reservoirs, we observed that it did not present satisfactory results, so specific models based on the MODIS red band were used to map TSS in each of the reservoirs. It can be concluded, therefore, that knowledge about the optical properties of water has proved to be determinant for the bio-optical modeling, especially with respect to highly contrasting environments such as BB and Nav. Keywords: bio-optical modeling, inland waters, remote sensing of water, reservoirs in cascade system LIST OF FIGURES Figure 2.1. Graphic representation of the study area emphasizing (a) Brazil’s territory, (b) Tietê River located at São Paulo State and the location of the reservoirs from upstream to downstream: Barra Bonita, Bariri, Ibitinga, Promissão, Nova Avanhandava and Três Irmãos, (c) sampling location of Nav and (d) BB. ........................................................................................................................................................ 25 Figure 2.2. Flowchart showing the methodological scheme for sampling stations definition. 𝜌𝑇𝑂𝐴 represents the value of reflectance at the top of atmosphere (TOA), SD stands for the standard deviation, NDWI is the Normalized Difference Water Index, and PCA is the Principal Component Analysis. The box 1 refers to the multispectral images; box 2 stands for the reservoir’s delimitation and box 3, stratified sampling. ............................................................................................................................................... 27 Figure 2.3. Rainfall data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). ............................................................................... 30 Figure 2.4. Water level data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Different axis y was used due to distinct magnitudes. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). .............. 31 Figure 2.5. Water flow data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). ............................................................................... 32 Figure 3.1. Relationship between water quality and optical parameters considering data from all field campaigns. (a) TSS versus Chl-a, (b) 𝑎𝜙(443) versus Chl-a, (c) 𝑎𝑁𝐴𝑃(443) versus TSS, (d) 𝑎𝐶𝐷𝑂𝑀(443) versus TSS and (e) 𝑎𝐶𝐷𝑂𝑀(443) versus Chl-a. ............................................................... 41 Figure 3.2. Ternary plot depicting the absorption coefficient budget of both Nav and BB reservoirs at three wavelengths: (a) 443 nm, (b) 560 nm and (c) 665 nm. ................................................................ 42 Figure 3.3. Variability of 𝑎𝐶𝐷𝑂𝑀by field trip. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝐶𝐷𝑂𝑀(𝜆) for each field trip. Different y axes were applied for Nav and BB due to magnitude discrepancies. ...................................................................................................................... 43 Figure 3.4. Variability of 𝑎𝜙by field trip. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝜙(𝜆) for each field trip. Different y axes were applied for Nav and BB due to magnitude discrepancies. ...................................................................................................................... 44 Figure 3.5. Variability of 𝑎𝑁𝐴𝑃(𝜆) in all field trips (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝑁𝐴𝑃(𝜆) for each field trip. ............................................................................. 45 Figure 3.6. Variability of 𝑎𝑝(𝜆) in all field trips. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝑝(𝜆) for each field trip. Different y axles were applied for Nav and BB due to magnitude discrepancies. ...................................................................................................................... 46 Figure 3.7. (a) Variation of 𝑎𝜙(𝜆)/𝑎𝜙(443) ratio as a function of wavelength considering the average values of BB and Nav and the mass-specific absorption of phytoplankton, 𝑎𝜙 ∗(𝜆), for all field campaigns (b) Nav1, (c) Nav2, (d) Nav3, (e) BB1 and (f) BB2. .......................................................... 49 Figure 3.8. (a) Variation of 𝑎𝑁𝐴𝑃(𝜆)/𝑎𝑁𝐴𝑃(443) ratio as a function of wavelength considering the averages values of BB and Nav and (b) the relationship between 𝑆𝑁𝐴𝑃and OSS (mg l-1) from BB. .... 51 Figure 4.1. Reciprocal remote sensing reflectance (𝑅𝑟𝑠 −1) data from the (a) first, (b) second and (c) third field trips. Pure water absorption (𝑎𝑤) (red line) is shown for reference. ............................................ 63 Figure 4.2. Ternary plots displaying the relative contribution of CDOM, phytoplankton and detritus to the total absorption at different wavelengths, (a) 443 nm, (b) 560 nm, (c) 665 nm and (d) the relative contribution of water, particulate and CDOM to absorption at 709 nm. ............................................... 64 Figure 4.3. Relationship between estimated and measured 𝑎𝑡(𝜆) using existing QAAs: (a) QAALv5, (b) QAALv6 and (c) QAAM14. The colored circles represents the band centers of OLCI sensor. ................ 66 Figure 4.4. Scatter plot between measured and estimated (a) 𝑎𝑡(𝜆), (b) 𝑎𝐶𝐷𝑀(𝜆) and (c) 𝑎𝜙(𝜆) at OLCI spectral bands. ....................................................................................................................................... 68 Figure 4.5. Taylor diagrams for 𝑎𝑡(𝜆) at (a) 443 nm, (c) 560 nm, (e) 665 nm. Target diagrams for 𝑎𝑡(𝜆) at (b) 443 nm, (d) 560 nm and (f) 665 nm. Color symbols indicate the following: QAALv5 (grey dot), QAALv6 (yellow dot), QAAM14 (blue dot) and the QAAOMR (green dot), reference observation (red dot). The black circle in the Target diagrams (M0) corresponds to a normalized total RMSD of 1.0, so all points between this circle and the origin are positively correlated. ...................................................... 70 Figure 4.6. Taylor diagrams for 𝑎𝐶𝐷𝑀(𝜆) at (a) 443 nm, (c) 560 nm, (e) 665 nm. Target diagrams for 𝑎𝐶𝐷𝑀(𝜆) at (b) 443 nm, (d) 560 nm and (f) 665 nm. Symbols indicate the following: QAALv5 (grey dot), QAALv6 (yellow dot), QAAM14 (blue dot) and the QAAOMR (green dot), reference observation (red dot). The black circle in the Target diagrams (M0) corresponds to a normalized total RMSD of 1.0. .......... 73 Figure 4.7. Taylor diagrams for 𝑎𝜙(𝜆) at (a) 443 nm, (c) 560 nm, (e) 665 nm. Target diagrams also for 𝑎𝜙(𝜆) at (b) 443 nm, (d) 560 nm and (f) 665 nm. Symbols indicate the following: QAALv5 (grey dot), QAALv6 (yellow dot), QAAM14 (blue dot) and the QAAOMR (green dot), reference observation (red dot). ............................................................................................................................................................... 76 Figure 4.8. Validation result showing the scatter plot between measured and estimated (a) 𝑎𝑡(𝜆), (b) 𝑎𝐶𝐷𝑀(𝜆), (c) 𝑎𝜙(𝜆) and the comparison of spectral shape of average measured and estimated (d) 𝑎𝑡(𝜆), (e) 𝑎𝐶𝐷𝑀(𝜆) and (f) 𝑎𝜙(𝜆). ................................................................................................................... 77 Figure 4.9. Graphic depicting the (a) rainfall, (b) runoff, (c) water level and (d) discharge variability along the period between October 2013 and August 2016. The green diamonds represent at(443) retrieved based on QAAOMR from the three field trips carried out in Nav during April/2014, September/2014 and May/2016. Rainfall data was acquired in NASA’s GIOVANNI database based on TRMM data with 0.25° of spatial resolution (http://giovanni.sci.gsfc.nasa.gov/giovanni/). Runoff data was also acquired through NASA’s GIOVANNI database. Water level as well as discharge were downloaded from the Water National Agency of Brazil through the website (http://sar.ana.gov.br/). . 80 Figure 4.10. Relationship between optical properties and water quality parameters: (a) 𝑎𝑡(443) versus TSS; (b) 𝑎𝐶𝐷𝑀(443) versus TSS; (c) 𝑎𝜙(443) versus TSS; (d) 𝑎𝑡(443) versus Chl-a; (e) 𝑎𝐶𝐷𝑀(443) versus Chl-a and (f) 𝑎𝜙(443) versus Chl-a. ......................................................................................... 82 Figure 5.1. Scatter plots in log-scale between measured and estimated 𝑎𝑡(𝜆), 𝑎𝐶𝐷𝑀(𝜆) and 𝑎𝜙(𝜆) at OLCI spectral bands. ............................................................................................................................. 89 Figure 5.2. Spectral shape acquired through (a) QAABBHR and (b) Nav in situ 𝑎𝜙 acquired from laboratory analysis. The continuous red line stands for the average spectral 𝑎𝜙 from Nav in situ data. ............................................................................................................................................................... 90 Figure 5.3. Scatter plots in log-scale between measured and estimated 𝑎𝑡(𝜆), 𝑎𝐶𝐷𝑀(𝜆) and 𝑎𝜙(𝜆) at OLCI spectral bands. ............................................................................................................................. 91 Figure 5.4. Spectral shape acquired through (a) QAAOMR and (b) in situ 𝑎𝜙 from BB acquired from laboratory analysis. The continuous red line stands for the average spectral 𝑎𝜙 from BB in situ data. 93 Figure 6.1. Schematic diagram showing the (a) viewing angle (𝜃𝑣) of the sensors to avoid specular scattering (Mobley, 1999) (b) Geometry of the sensor relative to the sun used for radiometric measurements, represented by zenith (𝜃𝑠), azimuthal (𝜙) and nadir (𝑛) angles, (c) sensors collecting total upwelling radiance 𝐿𝑡(𝜆), the incident sky radiance 𝐿𝑠(𝜆) and the downwelling irradiance 𝐸𝑑(𝜆), (d) sensors collecting upwelling radiance 𝐿𝑢(𝜆), upwelling irradiance 𝐸𝑢(𝜆) and the downwelling irradiance 𝐸𝑑(𝜆). ................................................................................................................................... 99 Figure 6.2. Cumulative percentage of TSM concentration and the respective frequency of the calibration dataset from BB (a) and Nav (b) reservoirs. ....................................................................................... 104 Figure 6.3. Relationship between TSM (mg l-1) and Chl-a (mg m-3) in (a) BB and (b) Nav. ............. 106 Figure 6.4. Ternary graphs depicting the absorption budget at three wavelengths in the visible region (a) blue – 443 nm, (b) green – 555 nm and (c) red – 645 nm. .................................................................. 107 Figure 6.5. 𝑅𝑟𝑠(𝜆)𝑓𝑖𝑒𝑙𝑑 spectra representing different TSM concentrations overlapped with MODIS Terra spectral response function for bands at (A) 469 nm, (B) 555 nm and (D) 645 nm. .................. 108 Figure 6.6. Correlation between the original 500 m MODIS B3 and the downscaled 250 m MODIS B3 for (a) May and (b) October, 2014. ..................................................................................................... 109 Figure 6.7. Spatio-temporal distribution of TSM over the main body of Nav based on MODIS 8-day composite images for months of May and October from 2000 to 2015. ............................................. 114 Figure 6.8. Spatio-temporal distribution of TSM over the main body of BB based on MODIS 8-day composite images for the months of May and October from 2000 to 2015. The blank region represent the locations where the model extrapolated the TSM values over 150 m l-1. ...................................... 115 Figure 6.9. TSM variability during the (a) beginning of the dry season and (b) end of the dry season in Nav; (c) beginning of the dry season and (d) end of the dry season in BB at different locations along the reservoir. SBS: Santa Barbara Stream, BR: Bonito River, PR: Piracicaba River, TR: Tietê River, TZ1: Tranzition Zone 1, TZ2: Transition Zone 2. (e) TSM (mg l-1) concentration from field campaigns carried out in Tietê River (Barra Bonita – BB, Bariri – B, Ibitinga – I, Promissão – P, Nova Avanhandava – Nav) except for Três Irmãos (TI) reservoir in 2000 (CAVENAGHI et al., 2003) (solid lines); including all reservoirs along the Tietê River during the years 2001 and 2002 (ZANATA, 2005) (dotted lines) and in the lower Tietê basin during 2008 and 2009 (dashed lines) (SANTOS, 2010). .............................. 118 LIST OF TABLES Table 3.1. Descriptive statistics of water quality and optical parameters. The notations Min- Max, Aver, SD, CV and n stand for minimum-maximum, average, standard deviation, coefficient of determination and number of samples. .............................................................. 39 Table 4.1. QAA steps comparing the version 5 from Lee et al. (2002) and the QAAOMR proposed in this study. .............................................................................................................................. 58 Table 4.2. Descriptive statistic of the water quality variables used for calibration and validation. SD: standard deviation, CV: coefficient of variation and n is the number of samples. ........... 61 Table 4.3. Comparative band-specific errors related to the re-parametrization of 𝑎𝑡(𝜆) based on MAPE (%) and RSMD (m-1) metrics. ...................................................................................... 68 Table 4.4. Comparative band-specific errors related to the re-parameterization of 𝑎𝐶𝐷𝑀(𝜆) based on MAPE (%) and RSMD (m-1) metrics. ....................................................................... 72 Table 4.5. Comparative band-specific errors related to the re-parametrization of 𝑎𝜙(𝜆) based on MAPE (%) and RSMD (m-1) metrics. ................................................................................. 75 Table 5.1 QAA steps comparing the QAABBHR from Watanabe et al. (2016) and the QAAOMR proposed in the last chapter. ..................................................................................................... 87 Table 5.2. Comparative band-specific errors related to the IOPs retrieved by QAABBHR based on MAPE (%), RSMD (m-1) and bias (m-1) metrics. ................................................................ 89 Table 5.3. Comparative band-specific errors related to the IOPs retrieved by QAAOMR based on MAPE (%), RSMD (m-1) and bias (m-1) metrics. ..................................................................... 92 Table 6.1. TSM empirical models: model fit, TSM concentration range (mg l-1), and geographic location. .................................................................................................................................. 102 Table 6.2. Descriptive statistics of environmental dataset in both reservoirs. ....................... 105 Table 6.3. Calibration results of the models using the single and two band indexes. Models with R² below 0.50 were not displayed here. ................................................................................. 110 LIST OF ABBREVIATIONS AND ACRONYMS 𝜌𝑇𝑂𝐴 Reflectance at the top of atmosphere 𝜁 𝑎𝜙(412)/𝑎𝜙(443) 𝜉 𝑎𝐶𝐷𝑀(412)/𝑎𝐶𝐷𝑀(443) 𝜂 Spectral power for backscattering coefficient 𝜆0 Reference wavelength 𝛿13𝐶 Delta thirteen carbon σ* Normalized standard deviation ap Total particulate absorption coefficient a or at Total absorption coefficient 𝑎𝑤 Absorption coefficient of pure water 𝑎𝑁𝐴𝑃 Absorption coefficient of non-algal particle 𝑎𝑑 Absorption coefficient of detritus 𝑎𝐶𝐷𝑂𝑀 Absorption coefficient of colored dissolved organic matter 𝑎𝐶𝐷𝑀 Absorption coefficient of CDOM and detritus 𝑎𝜙 Absorption coefficient of phytoplankton 𝑎𝑡−𝑤 Total absorption budget without the water fraction 𝑎𝜙 ∗ Specific absorption coefficient of phytoplankton 𝑎𝜙 + Normalized spectral absorption of phytoplankton 𝑏𝑏 Backscattering coefficient 𝑏𝑏𝑝 Particulate backscattering coefficient 𝑏𝑏𝑤 Pure water backscattering coefficient B* Normalized bias CDOM Colored dissolved organic matter Chl-a Chlorophyll-a 𝐸𝑢 Upwelling irradiance 𝐸𝑑 Downwelling irradiance IOP Inherent optical properties ISS Inorganic suspended solids 𝐿𝑢 Upwelling radiance 𝐸𝑑(0+) Downwelling irradiance incident onto the water surface 𝐿𝑠𝑘𝑦 Incident sky radiance 𝐿𝑡 Total upwelling radiance LULC Land use and land cover 𝑙 Path length MAPE Mean absolute percentage error MODIS Moderate Resolution Imaging Spectroradiometer NAP Non-algal particle NDWI Normalized Difference Water Index OSC Optically significant components OLCI Ocean and Land Colour Instrument OSS Organic suspended solids OD Optical density ODsample Optical density of the sample ODreference Optical density of the reference QAA Quasi-analytical algorithm 𝑅 Irradiance reflectance 𝑅𝑟𝑠 Remote sensing reflectance 𝑟𝑟𝑠 Subsurface remote sensing reflectance 𝑅𝑟𝑠𝑠𝑎𝑡 Water surface remote sensing reflectance 𝑅𝑟𝑠𝑠𝑖𝑚 Simulated bands from MODIS/Terra 𝑅𝑟𝑠𝑓𝑖𝑒𝑙𝑑 In situ remote sensing reflectance 𝑅𝑟𝑠 −1 Reciprocal remote sensing reflectance RMSD Total root mean square difference RMSE Total root mean square error 𝑆𝐶𝐷𝑀 Spectral slope of colored detrital matter absorption coefficient 𝑆𝐶𝐷𝑂𝑀 Spectral slope of colored dissolved organic matter 𝑆𝑁𝐴𝑃 Spectral slope of non-algal particle SIOP Mass-specific inherent optical properties SRF Spectral response function TSS Total suspended sediment or solids TSM Total suspended matter 𝑢 Ratio of backscattering coefficient to the sum of backscattering and absorption coefficients uRMSD* Normalized unbiased RMSD CONTENTS CHAPTER 1: INTRODUCTION ......................................................................................... 19 1.1 Background ................................................................................................................... 19 1.2 Motivation ...................................................................................................................... 20 1.3 Hypothesis ...................................................................................................................... 22 1.4 Objectives ...................................................................................................................... 23 1.5 Outline of the Thesis ..................................................................................................... 23 CHAPTER 2: STUDY AREA AND FIELD CAMPAIGNS ............................................... 24 2.1 General characteristics ................................................................................................. 24 2.2 Strategy for sampling design ....................................................................................... 26 2.3 Field campaigns ............................................................................................................. 29 2.4 Field data acquisition .................................................................................................... 32 CHAPTER 3: ABSORPTION PROPERTIES OF TWO OPTICALLY DIFFERENT RESERVOIRS SITUATED ALONG THE CASCADE SYSTEM OF TIETÊ RIVER .. 34 3.1 Introduction ................................................................................................................... 34 3.2 Data and Methods ......................................................................................................... 36 3.2.1 Water quality parameters ......................................................................................... 36 3.2.2 Inherent optical properties ........................................................................................ 37 3.3 Results ............................................................................................................................ 38 3.3.1 General characteristics of water quality parameters and optical properties ............. 38 3.3.2 Absorption coefficient budget .................................................................................. 41 3.3.3 CDOM absorption .................................................................................................... 42 3.3.4 Phytoplankton absorption ......................................................................................... 43 3.3.5 NAP absorption ........................................................................................................ 44 3.3.6 Particle absorption .................................................................................................... 45 3.4. Discussion ..................................................................................................................... 46 3.5 Conclusion ..................................................................................................................... 51 CHAPTER 4: RETRIEVAL OF INHERENT OPTICAL PROPERTIES FROM OLIGO-TO-MESOTROPHIC INLAND WATER USING THE QUASI-ANALYTICAL ALGORITHM ........................................................................................................................ 53 4.1 Introduction ................................................................................................................... 53 4.2 Data and methods ......................................................................................................... 55 4.2.1 Water quality parameters ......................................................................................... 55 4.2.2 In-Situ Radiometric Data .......................................................................................... 56 4.2.3 In Situ Inherent Optical Properties ........................................................................... 57 4.2.4 QAA General Context .............................................................................................. 58 4.2.5 Re-parametrization /Validation and Accuracy Assessment ..................................... 59 4.3 Results and Discussion .................................................................................................. 61 4.3.1 Biogeochemical characterization ............................................................................. 61 4.3.2 Bio-optical characterization ..................................................................................... 62 4.3.3 OSC relative contribution ........................................................................................ 63 4.3.4 Performance of existing QAA .................................................................................. 65 4.3.5 Re-parametrization of QAA to derive 𝑎𝑡 ................................................................. 66 4.3.6 Re-parametrization of QAA to derive 𝑎𝐶𝐷𝑀 ............................................................ 70 4.3.7 Re-parametrization of QAA to derive 𝑎𝜙 ................................................................ 73 4.3.8 Model Validation...................................................................................................... 76 4.3.9 Linking IOPs variability to physical and meteorological variation ......................... 78 4.3.10 Factors influencing optical changes in the reservoir .............................................. 81 4.3.11 Implications of QAAOMR for water resource management .................................... 83 4.4 Conclusion ..................................................................................................................... 83 CHAPTER 5: EVALUATION OF QAAOMR AND QAABBHR PERFORMANCES IN DERIVING THE IOPS IN BOTH BB AND NAV RESERVOIRS ................................... 85 5.1 Introduction ................................................................................................................... 85 5.2 Data and Methods ......................................................................................................... 86 5.3 Results and Discussion .................................................................................................. 88 5.3.1 Use of QAABBHR in Nav’s dataset ............................................................................ 88 5.4.2 Use of QAAOMR in BB’s dataset .............................................................................. 91 5.4. Conclusion .................................................................................................................... 93 CHAPTER 6: LONG-TERM MONITORING OF TOTAL SUSPENDED MATTER IN TROPICAL RESERVOIRS WITHIN A CASCADE SYSTEM WITH WIDELY DIFFERING OPTICAL PROPERTIES .............................................................................. 95 6.1 Introduction ................................................................................................................... 95 6.2 Data and Methods ......................................................................................................... 98 6.2.1 Field data .................................................................................................................. 98 6.2.2 Remote sensing reflectance (𝑅𝑟𝑠) ............................................................................. 98 6.2.3 Inherent Optical Properties (IOPs) ......................................................................... 100 6.2.4 Satellite Data and Processing ................................................................................. 101 6.2.5 Bio-optical model calibration and validation ......................................................... 102 6.3 Results .......................................................................................................................... 103 6.3.1 Long-term spatio-temporal monitoring .................................................................. 104 6.3.2 Water quality characterization ............................................................................... 104 6.3.3 Bio-optical properties description .......................................................................... 106 6.3.4 Downscaling MODIS image procedure ................................................................. 108 6.3.5 TSM algorithm calibration and validation ............................................................. 109 6.3.6 TSM spatio-temporal variability ............................................................................ 113 6.3.7 Factors affecting optical changes in the reservoirs ................................................ 119 6.4 Conclusion ................................................................................................................... 120 CHAPTER 7: CONCLUSION AND FUTURE RECOMMENDATIONS ..................... 122 7.1 Conclusion ................................................................................................................... 122 7.2 Future Recommendations .......................................................................................... 124 REFERENCES ..................................................................................................................... 126 Rodrigues, T.W.P. 19 CHAPTER 1: INTRODUCTION 1.1 Background The reservoirs of the Tietê River placed in the State of São Paulo, are exposed by a series of pollution sources such as sugar cane plantation, pastures and urban centers from which a large amount of pollutants reaches the aquatic system. On the one hand, the construction of these reservoirs supports the agriculture and industrial development of the region; on the other hand, it generates a series of negative impacts including intensive deforestation, eutrophication due to high loads of nutrients and suspended sediment from various activities, sedimentation and contamination of water bodies (BARBOSA et al. 1999). According to Fracácio et al. (2002), all the reservoirs of the Tietê River were classified as eutrophic for the parameter chlorophyll-a (Chl-a); for total phosphorus (TP), the reservoirs of Barra Bonita (BB), Bariri (B) and Ibitinga (Ib) were considered mesotrophic; and the Promissão (Pr) and Nova Avanhandava (Nav), oligotrophic. Differences in the mass of water composition between BB e Nav were reported and the first reservoir was attested to be more polluted than Nav. BB also has the highest concentration of suspended solids, thus higher turbidity when compared to Nav (CAVENAGHI et al. 2003). These results clearly show the existence of a trophic gradient between the cascade reservoirs. Although some studies have shown that the cascade reservoirs have a trophic and spectral gradient (WACHHOLZ et al., 2009; PEREIRA FILHO et al. 2009), just recently studies have investigated the cascade system effects on optical properties (ALCÂNTARA et al., 2016, RODRIGUES et al., 2016a). In terms of water resource management, the traditional methods for water monitoring are time consuming, expensive and demands in situ collection. Besides, these techniques present low spatial and temporal representativeness, therefore, the optical properties of the in-water constituents (Chl-a, non-algal-particle – NAP, total suspended sediment – TSS, colored dissolved organic matter – CDOM) and here known as optical significant components (OSCs), can be used in bio-optical models in order to estimate the concentrations of the OSCs and support the water resource management considering large areas and short time mapping. Rodrigues, T.W.P. 20 1.2 Motivation Environments such as reservoirs designed in cascade system cause water quality modifications from the upstream to downstream reducing the turbidity and increasing the transparency of water (BARBOSA et al. 1999). The longitudinal variability is not the only factor influencing the water quality dynamic, but the watershed controls several mechanisms of reservoirs functioning. Watersheds subjected to extensive use by human activities can produce high loads of nutrients, suspended matter or even toxic substances to the reservoir (JORGENSEN et al., 2012). Built to attend single or more specific purpose, the reservoirs have multiple uses and therefore, demands for complex strategies of management. The desired phases for management systems include the integration of geographic information system and remote sensing in order to provide a rapid or a large-scale comprehension of reservoirs (TUNDISI and MATSUMURA- TUNDISI, 2011). Remote sensing is also important for offering spatial and temporal views of water quality surface parameters, which is limited from in situ collections. Its applicability becomes useful when the water degradation is caused by OSC, such as the green algae pigments as Chl-a, TSS, CDOM and NAP, thus producing detectable effects by optical remote sensing instruments (GIARDINO et al., 2010). The spectral region where these components can be detected is limited to a narrow range of optical wavelengths, in general, restricted between 400 to 850 nm (DEKKER, 1993). In inland waters, NAP and CDOM absorb at shorter wavelengths showing an exponential decay toward longer wavelengths, while Chl-a presents absorption peaks in the blue and red wavelengths (ROESLER et al., 1989; BRICAUD et al., 1981). However, in waters with low phytoplankton concentration the absorption peak at the blue region is not detected (WU et al., 2011), nevertheless, significant contributions of Chl-a lead to the enhancement of the absorption peak at ~675 nm allowing its detection on the remote sensing reflectance (𝑅𝑟𝑠) signal in very productive inland waters (DOXARAN et al., 2006). Waters dominated by sediment, especially NAP and pure water showed satisfactory results with the empirical relationships 𝑅𝑟𝑠(850)/𝑅𝑟𝑠(550) and 𝑅𝑟𝑠(850)/𝑅𝑟𝑠(650) for TSS retrieval in Gironde estuary (DOXARAN et al., 2006). In waters comprised by mineral suspended sediment (MSS), the red-to-green ratio showed to be applicable, however, with increasing influence of phytoplankton and CDOM this relationship was found to break down, assuming the limited potential of the model (BINDING et al., 2003). In the case of CDOM absorption estimation, D’Sa and Miller (2003) showed that the ratio between two visible bands Rodrigues, T.W.P. 21 𝑅𝑟𝑠(510)/𝑅𝑟𝑠(555) was suitable for the turbid waters of Mississippi River, while Doxaran et al. (2006) found the ratio 𝑅𝑟𝑠(400)/𝑅𝑟𝑠(700) more appropriate for Tamar estuary. For Chl-a retrieval, Dall’Olmo et al. (2003, 2005) showed that a three-band model based on NIR-Red wavelengths produce more accurate values in turbid waters, however, they also noticed that both Chl-a fluorescence and Chl-a mass-specific absorption coefficient (𝑎𝐶ℎ𝑙𝑎 ∗ ) variability can introduce more uncertainties in the estimative. In other words, the knowledge about the optical water properties can improve the formulation of models for OSC concentration retrieval, however, algorithms based on empirical assumptions often fail when applied to other study sites (RITCHIE et al., 2003). Besides, these models are also limited for a specific range of OSC concentration. Kumar et al. (2016) for example, found a simple correlation between MODIS 𝑅𝑟𝑠(645 𝑛𝑚) and TSS concentration in Chilika Lagoon, India. Their model showed to be limited to the range between 6.5 and 200 mg l-1, with increasing error in very low TSS (< 6.54 mg l-1). Ogashawara et al. (2013) evaluated the influence of Chl-a absorption on the performance of several empirical algorithms using data from environments with very low and very high cyanobacteria. As result, they verified a decrease of model’s sensitivity in high phycocyanin concentration environments. Chen et al. (2015) studied a wide range of TSS (58 – 577.2 mg l-1) in estuary and coastal waters using an improved model based on the log-ratio (𝑅𝑟𝑠(𝑁𝐼𝑅)/𝑅𝑟𝑠(𝑅𝑒𝑑)), however, they had to consider a constraint based on TSS concentration below and above 31 mg l-1. In general, the empirical methods work well for turbid inland waters, however, in oligotrophic environments the performance decrease considerably using the same band combination. Gons et al. (2008) for example, showed that a red-to-NIR band Ch-a algorithm proved to be applicable for eutrophic to hypereutrophic waters, however the accuracy dropped considerably for oligotrophic waters. They also reported that remote sensing of Chl-a is limited in low concentration range and not the contrary. The alternative for low concentrations would be to use the blue-to-green band ratio (GONS and AUER, 2004; GONS et al., 2008). Aiming to address the empirical issue, semi-analytical approaches use the IOP and apparent optical properties (AOP) to model the reflectance and vice versa. These properties are then used in analytical methods to retrieve the water constituents. The main limitation regards the insufficient knowledge about the IOPs used in the equations (MOREL and GORDON, 1980; DEKKER, 1993). The example of a more robust model is the quasi-analytical algorithm (QAA) developed to derive the absorption and backscattering coefficients in open ocean and coastal waters (LEE et al., 2002). After that, several initiatives were carried out aiming to fit this model Rodrigues, T.W.P. 22 to productive inland waters (LE et al., 2009a; YANG et al., 2013, MISHRA et al., 2014; WATANABE et al., 2016a). A version based on CDOM dominated waters was also developed (OGASHAWARA et al., 2016), however, a model adapted to inorganic matter dominated water was not addresses yet. A semi-analytical algorithm using the QAA was successfully applied for retrieving the water clarity based on new theoretical model to interpret the Secchi disk depth, 𝑍𝑆𝐷 (LEE et al., 2015). For validation, the authors used data covering oceanic, coastal and inland waters (lake) and as result they got an average absolute difference of ~18%, highlighting the accomplishment of a model using a wide range of data. As previously mentioned, the comprehension about the bio-optical properties of different environments helps to indicate the suitable approach for water quality parameters estimation. Many efforts have shown the success of empirical approaches in deriving the water optical properties in very turbid inland waters, however, when data from two widely trophic state (oligo to eutrophic) reservoirs is supposed to be mixed, we expect the models to perform poorly, indicating the limitation of a single approach in retrieving the OSCs. Up to now, incipient initiatives showed the influence of cascade system in the optical properties, which means that a lot of efforts still need to be done. 1.3 Hypothesis In a cascading arrangement where the water flows with different composition through the system, the bio-optical modeling can be challenging. As we learned from the literature such systems range from hyper-to-oligotrophic, from organic-to-inorganic dominated waters, and consequently the development of an algorithm to map the water optical properties needs to deal with such contrast. Moreover, the literature showed that empirical models are constrained by the local optical properties and the range of OSC concentration, while semi-analytical approaches tend to fail where the phytoplankton is not the dominant component and where some empirical steps are calibrated using synthetic data. Thus, our hypothesis bases on the fact that due to the organic and inorganic nature of both BB and Nav reservoirs, the empirical approach won’t be able to map the OSC accurately using a single model, however, recalibrating the empirical steps using in situ data, the quasi-analytical algorithm will increase the retrieval of water optical properties and therefore will be able to map operationally the water quality from remotely sensed images in a cascade system. Rodrigues, T.W.P. 23 1.4 Objectives According to the thesis hypothesis, we aimed to investigate the water optical properties of both BB and Nav in order to evaluate the performance of a single model built for retrieving the inherent optical properties as well as total suspended sediment concentration of both reservoirs. For this, specific objectives were designed: - Characterize the absorption properties in both BB and Nav reservoirs; - Re-parameterize the QAA algorithm based on OLCI/Sentinel-3 bands using in situ data from Nav; validate the algorithm using an independent dataset collected from the same area in a different season; - Assess the performance of a single QAA version (QAABBHR from Watanabe et al. 2016 and QAAOMR proposed here) highlighting the improvements and fragilities from each version supposing to choose a single approach for mapping the absorption properties in the entire cascade; - Assess the performance of empirical models for retrieving TSS concentration in both BB and Nav using single or separate models. 1.5 Outline of the Thesis This thesis is organized in 7 chapters. Chapter 1 introduces the theme, highlighting the problem of the research followed by the questions we intend to answer and the objectives we expect to achieve. Chapter 2 describes the study areas focusing on their physical and environmental characteristics; description of the method designed to sampling definition and the field trips. Chapter 3 describes the IOPs of both reservoirs and their relationships with optical water parameters. In Chapter 4, a parametrization of QAAOMR was carried out using data from Nav and validate it with an independent dataset collected in a different season. Chapter 5 compares and evaluates the performance of both QAAOMR and QAABBHR in retrieving the IOPs using data from BB and Nav, respectively. In Chapter 6 empirical models were formulated aiming to retrieve TSS in both reservoirs. Lastly, Chapter 7 pointed out the main findings of the research and it makes some recommendations for future works. Rodrigues, T.W.P. 24 CHAPTER 2: STUDY AREA AND FIELD CAMPAIGNS 2.1 General characteristics The reservoirs of Barra Bonita (BB) and Nova Avanhandava (Nav) (Figure 2.1) are situated in the middle and lower portion of the Tietê River, São Paulo State, respectively. BB (22°31′10″S, 48°32′3″W) is a storage system and began its operation in 1963 flooding an area of 310 km2, with a dam length of 480 m, 90.3 days of residence time, being formed from the damming of Tietê and Piracicaba Rivers. The regional climate transits between tropical and subtropical, and the annual seasons are not well marked. According to the Koppen classification, the climate is mesothermal type - CWA, with a dry winter and a hot summer (PRADO, 2004). Pastures and sugar cane monoculture predominantly comprised the land cover. Rodrigues, T.W.P. 25 Figure 2.1. Graphic representation of the study area emphasizing (a) Brazil’s territory, (b) Tietê River located at São Paulo State and the location of the reservoirs from upstream to downstream: Barra Bonita, Bariri, Ibitinga, Promissão, Nova Avanhandava and Três Irmãos, (c) sampling location of Nav and (d) BB. On the other hand, Nav (21°7′1″S, 50°12′6″W) is a run-of-river reservoir and was created in 1982, flooding an area of 210 km² (at its maximum quota), with a dam length of 2,038 m and mean residence time of the water around 46 days (TORLONI, et al., 1993). The reservoir is part of a region whose influence of Continental Tropical and Polar Antarctic air masses are marked. The first mass is hot and dry and occurs mainly in the summer (24 and 30° Rodrigues, T.W.P. 26 C), while the second is cold and damp, and, despite being-active all year, its occurrence is more intense in winter, causing a decrease of temperature (22 to 14° C) (CBH-BT, 1999). BB reservoir is an ecosystem characterized as polymictic and eutrophic, with high loads of nutrients, whose contribution leads to the development of blooms of cyanobacteria during the summer, and Bacillariophyceae during the winter (DELLAMANO-OLIVEIRA et al. 2007). The Piracicaba and Tietê Rivers, which along their courses are subject to the carrying of organic and inorganic origin waste, arising from agricultural, urban and industrial activities, affecting water quality. Nav is an oligo-to-mesotrophic reservoir with the upper layer of the water column well oxygenated and pH ranging from slightly acid to alkaline (6.47 – 8.2), conductivity relatively high (83 – 150 µS cm-1) and low concentrations of nutrients (Total N: 0.05 – 0.23 µg l-1 and Total P: 18.02 – 32.33 µg l-1) (RODGHER et al. 2005; SMITH et al. 2014). The high transparency of the water often leads to the growth of submerged macrophytes (e.g. Egeria sp. – Elodea) (SMITH et al. 2014), although, during sample collections we avoided those areas. The catchment basin surrounding the reservoir receives input from non-point source of pollution such as sugar cane and citric plantation (orange and lemon) and cattle breeding. There is evidence that the downstream reservoirs of Tietê River have improved water quality to those further upstream providing an enhancement of chemical constitution of water limiting the development of floating vegetation representative of a eutrophic environment (BARBOSA et al., 1999; CAVENAGHI et al. 2003). The cascade system generates significant modifications along the river changing aspects such as heterogeneity, connectivity and the coarse / fine particulate organic material. Moreover, this type of system influences the water quality, the composition and structure of phytoplankton community, and increases the eutrophication process in the upstream reservoirs (BARBOSA et al., 1999). 2.2 Strategy for sampling design Based on the sampling design, a random stratified sampling method was used to determine the location for collecting water and optical data in BB and Nav (RODRIGUES et al., 2016b). Therefore, statistical and computational procedures were established aiming to provide parameters that subsidize the sampling design definition (Figure 2.2). For this purpose, the Operational Land Imager (OLI)/Landsat-8 imagery referring to an annual cycle was acquired at the USGS – U.S. Geological Survey website and the criterion of less cloud cover and absence of glint effect, visually detected, was applied. Rodrigues, T.W.P. 27 The images hosted at the USGS website are geometrically corrected and available for users in the orthorectified level (L1T) in which the reference data are terrain control points and altitude based on digital elevation model (DEM), such as the SRTM (Shuttle Radar Topography Mission) (USGS, 2014). This procedure assures the overlapping between images with geometric error below one pixel providing the high matching considering different periods. The methodological approach is displayed in Figure 2.2. Figure 2.2. Flowchart showing the methodological scheme for sampling stations definition. 𝜌𝑇𝑂𝐴 represents the value of reflectance at the top of atmosphere (TOA), SD stands for the standard deviation, NDWI is the Normalized Difference Water Index, and PCA is the Principal Component Analysis. The box 1 refers to the multispectral images; box 2 stands for the reservoir’s delimitation and box 3, stratified sampling. A set of images available for a year was radiometrically calibrated. In this process, the digital numbers (DN) of each pixel are rescaled for radiance or reflectance at the top of the atmosphere (TOA), 𝜌𝑇𝑂𝐴, using gain and offset parameters provided by the metadata of the image (USGS, 2013). This procedure removes the effects caused by the difference of Rodrigues, T.W.P. 28 illumination geometry (COLLETT et al., 1998). Studies carried out in aquatic systems showed that TOA products yielded similar or better results from those atmospherically corrected data (OLMANSON et al., 2011, KUTSER, 2012). In view of the hydrological dynamics and other anthropic or natural interventions that the reservoirs undergo over time, it is important to consider the variations in the chemical and biological characteristics of the water body, with the input of nutrients from agricultural activities around the reservoir, and still insertion of organic and inorganic substances carried longitudinally along the entire cascade system. Therefore, two statistical metrics were considered to analyze the variations: mean and standard deviation (SD). After the radiometric correction process, a set of images referring to one year (2013 - 2014), each consisting of 6 spectral bands (bands 2 to 7), were submitted to the calculation of the mean and subsequent standard deviation. Bands corresponding to the same wavelength were compressed and then the mean and standard deviation for the studied months were calculated, with each pixel of the final image having the mean value of spectral 𝜌𝑇𝑂𝐴, as well as standard deviation. For delimitation of the boundary of each reservoir a set of processes were established, such as the selection of a reference image, application of the NDWI, slice, conversion raster- vector e finally, the creation of the mask. The image of reference was based on the season with low rainfall. In this case, the image from July/2013 was chosen. It is worth mentioning that Nav does not present a notable variation in water level due to its operational system, on the contrary, BB varies seasonally. Aiming to separate water from other targets, NDWI from McFeeters (1996) was applied as follows: 𝑁𝐷𝑊𝐼 = 𝐺𝑟𝑒𝑛𝑛 − 𝑁𝐼𝑅 𝐺𝑟𝑒𝑒𝑛 + 𝑁𝐼𝑅 (2.1) where Green and NIR are the bands 3 and 5 from OLI/Landsat-8, respectively. This ratio aims to maximize the water reflectance in the visible spectral region and minimize it in the infrared. There are modifications of this index, such as the MNDWI proposed by Xu (2006) who used a ratio between the green and middle infrared (MIR) bands aiming to enhanced the features of water in regions which the contamination by other targets are evident like noises related to built-up land, soil and vegetation overestimating the water targets. However, we kept the Equation 2.1, since the method employed here predicts the use of a buffer in order to avoid the borders with other targets but water. The separation of water from the other targets was obtained by slicing between values representative of each target. Thus, pixels with values assigned with Rodrigues, T.W.P. 29 water were allocated in a class while the others in another class, resulting in two classes: water and non-water. For stratified sampling, the SD images were transformed in Principal Component Analysis (PCA) in a Geographic Information System (GIS) environment and then sliced according to intervals empirically defined. The selected image for this step was based on the component with higher variability from the set of 6 SD bands. The slice step allowed the creation of stratus for further sampling points definition. A buffer with 70 m was created for each reservoir to prevent the edges formed by land. Using the tool Hawth’s Tools developed by Hawthorne Beyer (http://www.spatialecology.com/) and compatible to a GIS environment, the random stratified sampling was possible to be carried out. Initially, more than a required number of samples were created in order to remove the non-spatialized stations. The minimal distance of 1 km between samples was established to prevent clusters. As result, 20 samples were acquired for each field campaign except for the third campaign in BB that included 4 samples (totalizing 24 samples) and in Nav 20 samples in different locations were added for the first and second field trips and 19 for the third field trip. 2.3 Field campaigns The water quality parameters, as well as their spatial distribution are seasonal dependent, therefore, we considered at least two periods of the year for water and optical data collection. The water samples were collected in six field campaigns (Figure 1). For Nav, the field trips occurred during austral autumn (Nav1: 28 April – 2 May/2014 and Nav2: 23 – 26 September/2014) and austral spring (Nav3: 9 and 14 May/2016). For BB, the field trips were carried out in austral autumn (BB1: 5 – 9 May/2014) and austral spring (BB2: 13 – 16 October/2014 and BB3: 13 – 15 September/2015). Both seasons are known for intermediate precipitation amounts between summer (wet period) and winter (dry period). Data collections were avoided in the summer due to high rainfall rates making difficult to obtain cloud free satellite images. As depicted in Figure 2.3, the rainfall data in BB and Nav showed distinct values. In Nav, for example, the month of January and February from 2011 to 2016 showed the highest averages values of 197.24 and 196.92 mm, respectively. BB, in turn, presented 222.59 and 209.16 mm in January and February, respectively. These values were expected because they occurred in the wet period (summer). The year of 2014 showed the lowest values for the respective months presenting 130.75 and 141.81 mm in Nav and 168.51 and 146.24 mm in BB, Rodrigues, T.W.P. 30 respectively. The lowest average values were observed in July and August corresponding to the dry period (winter). Nav showed in July and August averages of 42.51 and 12.79 mm, respectively, whilst BB presented averages of 72.85 and 46.29 mm. In 2014, the lowest rainfall in Nav were observed in June (24.00 mm) and August (6.80 mm) while in BB, the lowest ones were seen in July (40.26 mm) and August (38.83 mm). The months chosen for the field works varied below and above the mean measures (2011 – 2016), but in the austral summer of 2013/2014, the values were below the average and this happened due to an extreme event of drought classified as exceptionally dry (COELHO et al., 2015). The authors also described the 2014/2015 summer as atypical and dry, however, in lower magnitude as the 2013/2014 summer. The months of April/May of 2014 represented the period of the first data collection in Nav and the rainfall data showed that in both months the values (98.41 and 69.00 mm, respectively) were below the average between 2011 and 2016 (99.67 and 95.05 mm). The month of September/2014 related to the second field collection presented value (141.40 mm) above the average (86.14 mm) and the same happened to the third field trip (May/2016) which showed a value of 197.49 mm above the average (95.05 mm). Figure 2.3. Rainfall data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). Source: NASA/GIOVANNI (https://giovanni.gsfc.nasa.gov/giovanni/). The first field trip of BB carried out in May/2014 presented a value of 56.31 mm, below the average of 98.54 mm. The second field trip that occurred in October/2014, also exhibited a value (56.19 mm) below the average (164.14 mm). On the other hand, the third field trip (September/2015) displayed a value (192.08 mm) above the average (101.35 mm). The rainfall variability and the special event of dry in the austral summer (2013/2014) implied in severe Rodrigues, T.W.P. 31 impacts in water availability for public consumption, hydropower generation and agriculture (COELHO et al., 2015). Data of water level also showed the impact of the dry summer in 2014. A slight variability between 2011 to 2016 was observed in Nav (Figure 2.4), with an average interval of 357.60 ± 0.30 to 357.77 ± 0.32 m from January to December. The year of 2014 displayed the lowest water level except in January that showed a value of 357.56 m. The water level fluctuated between 0.13 m in 2011 to 0.69 m in 2015, in 2014 the amplitude was 0.50 m. Nav is a run-of- river reservoir, therefore, the water level variation with low amplitude is expected (PERBICHE- NEVES et al., 2013). Figure 2.4. Water level data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Different axis y was used due to distinct magnitudes. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). Source: National Water Agency – ANA (http://sar.ana.gov.br/MedicaoSIN) The water level in BB (Figure 2.4b) varied from an average of 447.85 ± 1.21 m in December and 451.10 ± 0.51 m in June. The year of 2014 was also the one with water level excepted for the months of January and February that was lower in 2015. The amplitude ranged between 2.11 m in 2013 to 9.84 m in 2015. 2014 presented an amplitude of 3.85 along the year. The storage or accumulation reservoir of BB generates a higher variation in water level than the run-of-river system (PERBICHE-NEVES et al., 2013). The water flow (Figure 2.5) also showed to vary as a function of the dry event in 2014, showing the lowest values in almost the entire year, except for January of 2015. Regarding the magnitude, Nav and BB presented significant differences, the variability in Nav, for instance, ranged from 232.09 m3/s in October to 683.34 m3/s in December, while in BB, the range was Rodrigues, T.W.P. 32 between 113.00 m3/s in October and 361.50 m3/s in December. The water flow was considerably reduced in BB aiming to keep the water retained in the system during the dry events, on the other hand, in Nav, the regulation of water flow, theoretically, is not necessary due to the absence of storage area, so the water flows naturally according to the river regime (EGRÉ and MILEWSKI, 2002). In addition, the regulation of Nav showed to be influenced by BB because of the variation in phase observed at Figure 2.5, highlighting the co-oscillation between them. Figure 2.5. Water flow data from the period between 2011 to 2016 (boxplots) highlighting the years of 2014, 2015 and 2016 for (a) Nav and (b) BB. Nav1 (28 April – 2 May/2014), Nav2 (23 – 26 September/2014) and Nav3 (9 and 14 May/2016). Source: National Water Agency – ANA (http://sar.ana.gov.br/MedicaoSIN) 2.4 Field data acquisition For this study both water quality and optical data were acquired for each sampling station. The amount of water collected for BB and Nav was established according to the total particulate matter capable to be filter without saturate it. Therefore, a total of 5L of water was collected for both reservoirs, however, for each TSS and Chl-a concentrations 250 – 500 mL were filtered considering one filter/replica in BB and 750 – 1000 mL were used for Nav. The water samples were stored in polyethylene containers and refrigerated for laboratory analysis. Water transparency was measured by a Secchi disk (30 cm diameter), turbidity by a portable turbidimeter, model Hanna HI 93414, and dissolved oxygen by a portable meter, model Hanna HI 9146-04. The in situ spectroradiometric measurements are very important for bio-optical characterization and information extraction from remote sensing data, as they act as a bridge Rodrigues, T.W.P. 33 between optical measurements in laboratory and measures taken at the orbital or airborne level. This kind of measure permits the elimination of some undesirable effects such as atmospheric influence and the scale effect. Thus, radiometric measurements were carried out through RAMSES-ARC (radiance sensors) and RAMSES-ACC (irradiance sensors) spectroradiometers. The RAMSES instruments provide simultaneous measurements of upwelling (𝐸𝑢) and downwelling (𝐸𝑑) irradiance and upwelling radiance (𝐿𝑢) of the water column as well as measurements of downwelling irradiance incident onto the water surface (𝐸𝑑(0+)), incident sky radiance (𝐿𝑠𝑘𝑦) and total upwelling radiance (𝐿𝑡) above the surface of the water. The determination of the total particulate absorption coefficient (ap = NAP + phytoplankton) was accomplished by the use of an integrating sphere module present in the double-beam Shimadzu UV-2600 UV-Vis spectrophotometer, with spectral sampling from 280 nm to 800 nm and spectral sampling of 1 nm. The pure water absorption coefficient is a constant obtained by Pope and Fry (1997). Rodrigues, T.W.P. 34 CHAPTER 3: ABSORPTION PROPERTIES OF TWO OPTICALLY DIFFERENT RESERVOIRS SITUATED ALONG THE CASCADE SYSTEM OF TIETÊ RIVER 3.1 Introduction Optical properties of water are the basis of watercolor retrieval algorithms. Variations of these properties can change the model parameters, optimal spectral bands and the accuracy of retrieval algorithms. In order to improve the performance of bio-optical models (semi- analytical approaches), a better understanding about the variability in the absorption (a, units in m-1) and backscattering (bb, units in m-1) coefficients is crucial. These coefficients influence the magnitude and the spectral distribution of the water-leaving reflectance. The a(λ) denotes the contribution of all components present in the aquatic system and is commonly represented into four additive elements, including the pure water (𝑎𝑤), NAP (𝑎𝑁𝐴𝑃), CDOM (𝑎𝐶𝐷𝑂𝑀) and phytoplankton (𝑎𝜙), all dependent on wavelength (BABIN et al., 2003; BINDING et al., 2008). In case of pure water, the absorption starts to increase from green to near-infrared (NIR) wavelengths (SMITH and BAKER, 1981). CDOM can remove the blue light in the first layer of the water and exhibit an exponential decrease with increasing wavelength; however, the shape is not equal for all waters (DEKKER, 1993). In order to describe the spectral CDOM absorption, Bricaud et al. (1981) came up with the following model: 𝑎𝐶𝐷𝑂𝑀(𝜆) = 𝑎𝐶𝐷𝑂𝑀(𝜆0)𝑒−𝑆𝐶𝐷𝑂𝑀(𝜆−𝜆0) (3.1) where 𝜆0 is a reference wavelength, 𝑎𝐶𝐷𝑂𝑀(𝜆0) is the absorption estimate at a reference wavelength, and 𝑆𝐶𝐷𝑂𝑀 is the spectral slope of the 𝑎𝐶𝐷𝑂𝑀(𝜆). The former provides insights about the characteristics of CDOM in terms of chemistry, source and diagenesis (HELMS et al., 2008) and is also a proxy for CDOM composition such as the ratio of fulvic to humic acids and molecular weight (SHANMUGAM et al., 2011). Besides, it is strongly dependent on the wavelength interval chosen for analysis (ROESLER et al., 1989; LOISELLE et al., 2009). The NAP also presents an exponential decrease from short to longer wavelengths and is represented by the spectral slope, 𝑆𝑁𝐴𝑃, which is related to the fraction of organic and inorganic matter (BABIN et al., 2003). Meanwhile, phytoplankton presents two distinct absorption features at 443 and 675 nm. Its composition is clearly defined by the water quality and its abundance is essentially determined by the underwater light and nutrient loading (DEKKER, 1993). Rodrigues, T.W.P. 35 The characterization of IOP in ocean and coastal waters have been massively studied in the last four decades, therefore, the comprehension about the relationship between in-water constituents and optical properties are well known (MOREL and MARITORENA, 2001; BABIN et al., 2003). In open ocean, for example, the influence of terrigenous matter is negligible and is assumed that only phytoplankton domain the optical properties as well as the pure water (MOREL and BRICAUD, 1986). In contrast, the inland waters are considered complex environments due to the increased number of color-producing agents and the high variability in their concentrations, limiting the use of empirical oceanic algorithms for Chl-a retrieval, for example (BUKATA, 2005). More robust models such as the semi-analytical and analytical approaches require the knowledge about the mass-specific inherent optical properties (SIOPs), like those used by Lee et al. (2002) with the QAA and the Garver-Siegel-Maritorena algorithm (GARVER and SIEGEL, 1997; MARITORENA et al., 2002). The SIOPs are retrieved by normalizing the absorption coefficient of a certain OSC and the respective concentration. The mass-specific phytoplankton absorption (𝑎𝜙 ∗ ), for example, is related to phytoplankton cell size, accessory pigments and package effect (BRICAUD et al., 1995; BABIN et al., 2003). Registers of the (S)IOPs in inland waters are available for specific regions around the world such as in Babin et al. (2003) who studied the coastal waters around Europe; Binding et al. (2008) produced a data set of absorption coefficients in Lake Erie; Perkins et al. (2009) documented the spectral features, magnitudes and variability of the IOPs in Finger Lakes of New York; Le et al. (2009b) investigated the variations of absorption and total specific absorption coefficient of phytoplankton in Lake Taihu, China; Campbell et al. (2011) described the SIOPs of three sub-tropical and tropical waters reservoirs in Australia; Wu et al. (2011) estimated the absorption and backscattering coefficients in Poyang Lake, China and analyzed their relations to the main water constituents; Matthews and Bernard (2013) presented the absorption properties of phytoplankton, CDOM and NAP for three small optically-diverse South African inland waters; Ylöstalo et al. (2014) characterized variations of different absorption components between different lake types and seasons in various lakes in the boreal region, in turn, Riddick et al. (2015) showed the spatial variability of absorption coefficients over a biogeochemical gradient in Lake Balaton, Hungary. Many efforts have been done from the last decade regarding the studies of (S)IOPs in inland waters, however, much more is expected to be done in order to cover a variety of environments and provide subsides to understand how these properties influence the Rodrigues, T.W.P. 36 parameterization of bio-optical models aiming to assist the remote-sensed-based monitoring of water quality. Environments such as reservoirs designed in a cascade system, for example, causes limnological modifications from the upstream to downstream reducing the turbidity and increasing water clarity (BARBOSA et al., 1999). The (S)IOPs can be somehow modulated by biogeochemical filtration from the first to the last reservoirs. The current study aims to characterize two optically different reservoirs situated along the cascade system of Tietê River, whose influence are dictated by the watershed dynamic, in order to improve the knowledge about bio-optical properties of a system covering two distinct trophic states (oligo to hypereutrophic) and to raise the main sources of spatial variability in the IOPs. 3.2 Data and Methods For this study, data from all the field trips were used. The campaigns of BB were named as BB1, BB2 and BB3 standing for the sequence of field campaigns realization. For Nav, the campaigns were identified as Nav1, Nav2 and Nav3. The number of samples used for this chapter is displayed in Table 3.1. 3.2.1 Water quality parameters To determine the TSS concentration we applied the method described by APHA (1998). The water volume was filtered on the same day of collection through pre-ashed and pre-weighed Whatmam fiberglass GF/F filter with a nominal porosity of 0.7 μm and then stored at the refrigerator until analysis. The filters were dried in 100° C oven for 12h, and then weighted in an analytical balance. To retrieve the inorganic suspended sediment (ISS), the filter dried and weighed in the last step was subjected to a muffle furnace for 75 min at 550° C and weighted again. As result, we determined the TSS, ISS and to estimate the organic suspended sediment (OSS), the last weighted filter was subtracted to the original filter weight after first drying. The analysis to determine the Chl-a concentration was based on Golterman et al. (1978). The specified volume of water was filtered under low vacuum pressure through a Whatman fiberglass GF/F filter with a porosity of 0.7 μm, and then frozen for laboratory analysis for no longer than 1 week. The chlorophyll was extracted by maceration in 90% acetone, then stored in 20 mL tubes and centrifuged. Afterward, one sample was placed in 1 cm quartz cuvette and to represent the reference a volume of acetone was placed in another cuvette. The readings were made in a spectrophotometer at 663 nm indicating the maximum absorption of chlorophyll in Rodrigues, T.W.P. 37 acetone and at 750 nm characterizing the absorption by chlorophyll and pheophytin. After this reading, 0.1N hydrochloric acid was added to the sample in order to remove magnesium from the chlorophyll and convert it into pheophytin and another reading was taken. 3.2.2 Inherent optical properties To estimate the CDOM absorption coefficient, 𝑎𝐶𝐷𝑂𝑀(𝜆), a volume of water was filtered through a fiberglass Whatman GF/F with porosity of 0.7 μm, and then re-filtered under low vacuum pressure using a nylon membrane filter with porosity of 0.2 μm. The readings were performed using Shimadzu UV-2600 UV-VIS spectrophotometer (SHIMADZU, Japan) in absorbance mode, and the samples were placed in 10 cm quartz cuvettes. For each set of measurements, we performed a reference reading containing Milli-Q water, and for each read sample (𝑂𝐷𝑠𝑎𝑚𝑝𝑙𝑒), the reference absorbance value was subtracted (𝑂𝐷𝑟𝑒𝑓). The measured optical densities (𝑂𝐷𝑠𝑎𝑚𝑝𝑙𝑒) were converted to absorption coefficient by multiplying by 2.303 and dividing by the path length (l = 0.1 m for a 10 cm cuvette). Therefore, the 𝑎𝐶𝐷𝑂𝑀(𝜆) was estimated following the equation (TILSTONE et al., 2002): 𝑎𝐶𝐷𝑂𝑀(𝜆) = 2.303 𝑂𝐷𝑠𝑎𝑚𝑝𝑙𝑒 𝑙 = 2.303 𝑂𝐷𝑠𝑎𝑚𝑝𝑙𝑒 0.1 (𝑚−1) (3.2) The 𝑎𝐶𝐷𝑂𝑀(𝜆) follows an exponential function decreasing from the visible to longer wavelengths. The data adopted to fit to the nonlinear regression ranged from 350 and 500 nm (BABIN et al., 2003). Twardowski et al. (2004) highlighted the main issues related to the spectral variability found in the results of many studies and attribute to the spectral range used in the adjustment. The 𝑆𝐶𝐷𝑂𝑀 can be used to understand the composition of CDOM (GREEN and BLOUGH, 1994, TWARDOWSKI et al., 2004). Absorption measures may contain errors related to the scattering of small particles or colloids that can cross the filters, leading some researchers to use equations to correct these effects (BRICAUD et al., 1981, GREEN and BLOUGH, 1994, BABIN et al., 2003). In order to turn the results comparable, the procedure described by Babin et al. (2003) were adopted in this study. For particulate absorption coefficients, water samples were filtered at low vacuum pressure using a 47 mm diameter fiberglass Whatman GF/F filter. The filters were wrapped in aluminum foil and frozen until laboratory analysis. A white filter wetted with ultrapure water was used as reference and the filter containing the particulate was placed on the integrating Rodrigues, T.W.P. 38 sphere module presented in the double-beam Shimadzu UV-2600 UV-VIS spectrophotometer (SHIMADZU, Japan) with spectral sampling ranging from 280 – 800 nm, to measure their optical density (OD). The T-R (Transmittance-Reflectance) method described by Tassan and Ferrari (1995, 1998) was employed to derive the total particulate absorption coefficient (𝑎𝑝). The particulate filter was submitted to depigmentation by oxidation in 10% sodium hypochlorite (NaClO), ensuring free phytoplankton influence to obtain 𝑎𝑁𝐴𝑃. The 𝑎𝜙 was retrieved by subtracting the 𝑎𝑁𝐴𝑃 from the 𝑎𝑝. 𝑎𝜙(𝜆) = 𝑎𝑝(𝜆) − 𝑎𝑁𝐴𝑃(𝜆) (3.3) The 𝑎𝜙 ∗ (𝜆) was obtained by normalizing the absorption due to phytoplankton by the Chl-a concentration. Babin et al. (2003) highlight that 𝑎𝜙 includes absorption related to all pigments, incorporating phaeopigment associated with other particles other than living phytoplankton. The 𝑎𝑁𝐴𝑃 can be adjusted by Roesler et al. (1989): 𝑎𝑁𝐴𝑃(𝜆) = 𝑎𝑁𝐴𝑃(𝜆0)𝑒−𝑆(𝜆−𝜆0) (3.4) The fit of the model was carried out between 350 and 800 nm, excluding the interval between 400 – 480 and 620 – 710 nm related to the absorption of some type of pigment interval that may have remained after depigmentation (BABIN et al., 2003). 3.3 Results 3.3.1 General characteristics of water quality parameters and optical properties The water quality parameters as well as the optical properties were all analyzed in terms of field trips (Table 3.1). Thus, the average turbidity between BB1 and BB2 was statistically different (p-value < 0.05) and the same happened between BB2 and BB3. On the other hand, data from BB1 and BB3 were not statistically different (p-value > 0.05). The same result was also observed for Chl-a and TSS concentrations. The increase of Chl-a concentration in October of 2014 was due to the drought effect leading to flow reduction and longer retention time (WATANABE et al., 2016b). High values of Chl-a for BB revealed the eutrophication status of the water, mainly in the winter (LUZIA, 2004). In Nav, the average turbidity from Nav1 and Rodrigues, T.W.P. 39 Nav2 was not considered statistically different (p-value > 0.05), however, the average Chl-a concentration from all three field trips was statistically different. The average TSS from Nav1 and Nav2 was not different, but this was not true when data from Nav2 was compared to Nav3 and Nav1 with Nav3. Assessing both reservoirs, we clearly observe that BB is more turbid due to high contribution of phytoplankton mainly in the BB2 that achieved a Chl-a value of 797.80 μg l-1 close to the dam. On the contrary, Nav presented low concentrations of Chl-a, where the average did not exceed 9.0 μg l-1 for Nav1 and Nav2 but reached 26.4 μg l-1 in Nav3, where the samples were concentrated at the upstream region of the reservoir. The variation of water quality parameters was strictly related to rainfall condition as well as the location of each reservoir in the cascade system. The analysis of individual reservoirs cannot provide the necessary information about the water quality dynamic, because this kind of structure cause discontinuity in the physical and biological features (BARBOSA et al., 1999). Table 3.1. Descriptive statistics of water quality and optical parameters. The notations Min- Max, Aver, SD, CV and n stand for minimum-maximum, average, standard deviation, coefficient of determination and number of samples. Blank spaces represent lack of data. Nav1 Nav2 Nav3 BB1 BB2 BB3 Chl-a (μg l-1) Min–Max 2.5–12.6 4.5–20.5 15.8–38.6 17.8–279.9 263.2 – 797.8 62.8–245.7 Aver ± SD 6.2±2.5 9.0±4.1 26.4±6.7 120.4±68.5 428.7±154.5 127.1±51.3 CV (%) 40.0 45.5 25.3 56.9 36 40.4 n 20 19 10 20 20 24 TSS (mg l-1) Min–Max 0.1–2.6 0.5–2.8 1.9–5.3 3.6–16.3 10.8–44.0 1.6–8.4 Aver ± SD 1.0±0.6 1.0±0.6 3.1±1.0 7.2±3.9 22.0±7.0 5.6±1.8 CV (%) 61.7 56.2 32.4 44.1 32.1 32.0 n 17 19 10 20 20 24 OSS (mg l-1) Min–Max - - - 2.8–14.7 10.2–30.4 - Aver ± SD - - - 6.1±2.6 18.2±3.5 - CV (%) - - - 41.9 19.3 - n - - - 20 19 - Turbidity (NTU) Min–Max 1.0–2.5 1.0–2.6 - 1.7–12.5 11.6–33.2 3.1–6.8 Aver ± SD 1.7±0.4 1.7±0.4 - 5.8±2.4 18.6±5.3 4.2±0.8 CV (%) 25.4 22.9 - 45.8 28.3 20.3 n 20 19 - 20 20 24 SDD (m) Min–Max 2.3–4.8 2.5–4.7 1.9–3.8 0.8–2.3 0.4–0.8 1.0–1.6 Aver ± SD 3.2±0.6 3.4±0.6 3.0±0.6 1.5±0.4 0.6±0.1 1.3±0.2 CV (%) 20.0 17.6 21.0 28.2 17.2 16.6 n 20 19 18 20 20 24 Depth (m) Min–Max 5.3–30.0 - 7.4–32.9 10.0–30.0 8.0–18.5 9.6–26.0 Aver ± SD 18.0±8.3 - 22.9–6.8 15.4±4.1 13.0±2.7 16.3±3.7 CV (%) 46.2 - 29.8 26.5 21.0 22.5 n 20 - 18 19 20 24 𝒂𝝓(𝟒𝟒𝟑) (m-1) Min–Max 0.1–0.4 0.1–0.4 0.1–0.6 0.3–2.4 - - Aver ± SD 0.2±0.1 0.2±0.1 0.3±0.1 1.1±0.6 - - CV (%) 39.1 40.8 43.5 52.1 - - n 20 20 19 20 - - Min–Max 0.1–0.5 0.1–0.7 0.4–0.8 0.3–0.8 - - Rodrigues, T.W.P. 40 𝒂𝑵𝑨𝑷(𝟒𝟒𝟑) (m-1) Aver ± SD 0.3±0.1 0.3±0.1 0.6±0.1 0.5±0.1 - - CV (%) 25.8 52.0 19.6 25.4 - - n 20 20 19 20 - - 𝒂𝑪𝑫𝑶𝑴(𝟒𝟒𝟑) (m-1) Min–Max 0.2–0.3 0.2–0.5 0.06–0.09 0.6–1.1 - - Aver ± SD 0.3±0.0 0.3±0.1 0.08±0.01 0.7±0.1 - - CV (%) 8.5 17.0 8.9 14.2 - - n 20 19 19 20 - - Water quality properties such as TSS and Chl-a as well as the IOPs at 443 nm were plotted against each other aiming to provide the main constitution of both reservoirs. No significant linear relationship (p-value > 0.05) was observed between TSS and Chl-a (Figure 3.1a) for Nav considering a log scale (Nav1: R = 0.44; Nav2: R = -0.18; Nav3: R = 0.42), which means that Nav is not dominated by phytoplankton. However, for BB, there is a significant relationship for all three field trips (BB1: R = 0.75, p-value < 0.001; BB2: R = 0.60, p-value < 0.05; BB3: R = 0.74, p-value < 0.001) showing that phytoplankton was the main contributor of TSS. 𝑎𝜙(443) and Chl-a concentration (Figure 3.1b) did not show significant relationship (p- value > 0.05) for Nav1 (R = 0.42) and Nav2 (R = -0.22) on the other hand, for Nav3, we observed a strong linear relationship (R = 0.81, p-value < 0.05). For BB, the correlation was statistically significant for both BB1 (R = 0.92, p-value < 0.001) and BB2 (R = 0.52, p-value < 0.05). As reported by Le et al. (2015), the strong correlation between 𝑎𝜙(443) and Chl-a is associated with high loads of nutrients in the aquatic system increasing phytoplankton production. According to Luzia (2004), the limiting nutrient that controls the growth of aquatic plants in majority of fresh waters is the inorganic form of phosphorus. Considering the relationship between 𝑎𝑁𝐴𝑃(443) and TSS (Figure 3.1c) for Nav, it was difficult to notice any relationship (Nav1: R = 0.27; Nav2: R = -0.11; Nav3: R = 0.33, p-value > 0.05). For BB, the non-correlation was also observed for both field trips (BB1: R = -0.05; BB2: R = -0.37, p-value > 0.05). Now considering the relationship between 𝑎𝐶𝐷𝑂𝑀(443) and Chl-a (Figure 3.1d) for Nav, again, no correlation was observed in any of the three campaigns (Nav1: R = 0.14; Nav2: R = 0.15; Nav3: R = 0.17, p-value > 0.05), while for BB1 the relationship was significant (R = 0.77, p-value < 0.001) and weak for BB2 (R = 0.25, p-value > 0.05). Regarding the relationship between 𝑎𝐶𝐷𝑂𝑀(443) and TSS (Figure 3.1e), Nav did not show any statistical correlation (Nav1: R = -0.06; Nav2: R = -0.18; Nav3: R = 0.14, p-value > 0.05) whilst BB1 showed to be moderately (R = 0.53, p-value < 0.05) and weakly correlated for BB2 (R = 0.19, p-value > 0.05). The non-correlation combined with the low Chl-a in Nav can indicate that TSS and CDOM were possibly originated from land-based sources and not from phytoplankton degradation. Rodrigues, T.W.P. 41 Figure 3.1. Relationship between water quality and optical parameters considering data from all field campaigns. (a) TSS versus Chl-a, (b) 𝑎𝜙(443) versus Chl-a, (c) 𝑎𝑁𝐴𝑃(443) versus TSS, (d) 𝑎𝐶𝐷𝑂𝑀(443) versus TSS and (e) 𝑎𝐶𝐷𝑂𝑀(443) versus Chl-a. 3.3.2 Absorption coefficient budget The relative contribution of phytoplankton, CDOM and NAP relative to the total absorption without the water fraction (𝑎𝑡−𝑤) can be seen in Figure 3.2. The wavelengths chosen for analysis (443, 560 and 665 nm) characterize the light interaction with dissolved organic matter and particulate matter (BABIN et al., 2003; LE et al., 2013). The ternary plots show the contribution and representativeness of certain OSC in the water and can be used to assist the estimation of these components using proper algorithms (MISHRA et al., 2014; RIDDICK et al., 2015). Figure 3.2(a) shows that at 443 nm, Nav1 was dominated by 𝑎𝑁𝐴𝑃 with 43.24 ± 6.52 %, Nav2 by 𝑎𝐶𝐷𝑂𝑀 with 37.89 ± 9.22 %, Nav3 by 𝑎𝑁𝐴𝑃 62.17 ± 9.39 %. At 560 nm (Figure 3.2b), Nav1, Nav2 and Nav3 were all dominated by 𝑎𝑁𝐴𝑃 with 48.57 ± 7.42 %, 46.87 ± 10.11 % and 72.14 ± 13.70 %, respectively. At 665 nm (Figure 3.2c), all three field trips were dominated by 𝑎𝜙 (Nav1: 55.00 ± 8.95 %, Nav2: 39.72 ± 12.06 % and Nav3: 65.16 ± 12.39 %). As expected, the most dominant OSC in the absorption budget considering both field trips and wavelengths in BB was the phytoplankton. At 443 nm (Figure 3.2a), BB 1 and BB 2 Rodrigues, T.W.P. 42 were dominated by 𝑎𝜙 with a percentage of 45.72 ± 12.71 % and 72.38 ± 9.36 %. At 560 nm (Figure 3.2b), the 𝑎𝜙 of BB 1 and BB 2 presented a percentage of 41.98 ± 13.43 % and 63.33 ± 13.75 %, respectively while at 665 nm (Figure 3.2c), the contribution was over 80% (BB 1 = 85.38 ± 6.80 % and BB 2: 87.90 ± 6.38 %). Figure 3.2. Ternary plot depicting the absorption coefficient budget of both Nav and BB reservoirs at three wavelengths: (a) 443 nm, (b) 560 nm and (c) 665 nm. 3.3.3 CDOM absorption The 𝑎𝐶𝐷𝑂𝑀 spectra approached to zero close to 700 nm and showed an exponential decrease pattern from shorter to higher wavelengths (BRICAUD et al., 1981) with values at 443 nm ranging between 0.06 to 0.45 m-1 in Nav and between 0.62 to 2.34 m-1 in BB (Figure 3.3). The magnitude differs from one reservoir to another as well as from one season to another. Values from BB are like those found by Matthews and Bernard (2013), who stated an interval between 0.63 to 4.13 m-1 in three South African reservoirs. Wu et al. (2011) found values ranging between 0.33 to 1.01 m-1 in Poyang Lake, China, considered a suspended inorganic matter dominated water with low Chl-a concentration (1.47 – 24.65 μg l-1) while Campbell et al. (2011) reported an interval of 0.36 and 1.59 m-1 in three Australian reservoirs. Zhang et al. (2007) observed in Lake Taihu values ranging between 0.27 to 2.36 m-1. Binding et al. (2008) reported values at 440 nm ranging between 0.08 to 0.75 m-1 in Lake Erie (Canada/USA) that was close to that found in Nav. The mean value for the spectral slope of CDOM (𝑆𝐶𝐷𝑂𝑀) was 0.018 nm-1 for BB1 and 0.016 nm-1 for BB2, whilst for Nav1 the mean 𝑆𝐶𝐷𝑂𝑀 was 0.020 nm-1 and 0.018 nm-1 for Nav2 and Nav3. Riddick et al. (2015) also found a mean 𝑆𝐶𝐷𝑂𝑀 of 0.018 nm-1 in Kis-Balaton (wetland system) and 0.020 nm-1 in the Lake Balaton (freshwater lake in central Europe). On the other hand, Babin et al. (2003) reported a narrow range around 0.0176 Rodrigues, T.W.P. 43 nm-1 in coastal waters around Europe. The authors highlighted that diverse protocols to retrieve 𝑆𝐶𝐷𝑂𝑀 can make it difficult to compare values from different regions. Figure 3.3. Variability of 𝑎𝐶𝐷𝑂𝑀 by field trip. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝐶𝐷𝑂𝑀(𝜆) for each field trip. Different y axes were applied for Nav and BB due to magnitude discrepancies. 3.3.4 Phytoplankton absorption Figure 3.4 depicts the 𝑎𝜙 spectra between 400 to 700 nm. The magnitude and shape are different when we compare both reservoirs and this can be due to the diversity of trophic states and phytoplankton assemblages (MATTHEWS and BERNARD, 2013). The peaks at the blue and red regions are consistent with the typical diagnostic features of phytoplankton absorption (WU et al., 2011). At 440 nm, accessory pigments and Chl-a contribute with high absorption, while at 675 nm, Chl-a plus phaeophytin are primarily responsible for high absorption (SATHYENDRANATH et al., 1987; LE et al., 2009b). Other pigments such as carotenoids absorb from 460 to 490 nm, however, this feature is not prominent in Nav neither BB. The absolute intervals of absorption at 443 nm are 0.05 – 0.57 m-1 for Nav and 0.27 – 10.34 m-1 for BB. Roesler et al. (1989) found values at 400 nm between 0.03 to 0.58 m-1 in inland marine waters in the USA, which was very close to that found in Nav. High values were reported in many turbid inland waters with characteristics close to that presented in BB (WU et Rodrigues, T.W.P. 44 al., 2011, MATTHEWS and BERNARD, 2013, MISHRA et al., 2014). 𝑎𝜙 at 443 nm exhibited an increased trend from the first to the second field campaigns, and the same happened for Nav considering the first to the third field trips. Mean 𝑎𝜙(620) ranged from 0.33 to 1.47 m-1 in BB and 0.04 to 0.10 m-1 in Nav. Chl-a concentration showed a strong relationship with 𝑎𝜙(620) and BB1 (R² = 0.80, p < 0.001, not presented here) but no correlation was found with BB2 (R² = 0.11, p > 0.05) as well as with Nav considering all three field trips (p > 0.05). The pigment phycocyanin, when present, can be detected through the 𝑎𝜙 spectrum especially at 620 nm. This pigment is a marker for cyanobacteria in eutrophic inland waters (SIMIS et al., 2005). Figure 3.1(b) showed the non- relationship between 𝑎𝜙(443) and Chl-a in Nav, suggesting that Chl-a was not the only pigment affecting 𝑎𝜙, but other accessory pigments, such as carotenoid (WU et al., 2011). Figure 3.4. Variability of 𝑎𝜙 by field trip. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝜙(𝜆) for each field trip. Different y axes were applied for Nav and BB due to magnitude discrepancies. 3.3.5 NAP absorption The spectral shape of 𝑎𝑁𝐴𝑃 (Figure 3.5) is quite similar of 𝑎𝐶𝐷𝑂𝑀 with an exponential decrease from 400 to 700 nm. Visually, the seasonal pattern between field campaigns and reservoirs did not show remarkable changes as reported previously. Taking into account the data from Nav, we observed that at 443 nm the values varied from 0.13 to 0.82 m-1 with averages varying from 0.33 m-1 in Nav1, 0.27 m-1 in Nav2 and 0.61 m-1 in Nav3, showing that 𝑎𝑁𝐴𝑃(443) Rodrigues, T.W.P. 45 increased in Nav3. Sample 5 from Nav2 stood out from the dataset because of the presence of sand dredging activity in that region leading to sediment resuspension. Meanwhile, BB showed a range of 0.23 to 1.67 m-1 with averages varying from 0.45 m-1 in BB1 and 0.47 m-1 in BB2. Samples 17 to 20 placed at Tietê River and confluence of Tietê and Piracicaba Rivers presented the highest values for 𝑎𝑁𝐴𝑃(443). These regions receive high loads of sediment from the metropolitan region of São Paulo. The mean slope (𝑆𝑁𝐴𝑃) of BB1 and BB2 was 0.007 and 0.008 nm-1, respectively, ranging between 0.006 to 0.01 nm-1 while for Nav the mean values were 0.009, 0.006 and 0.007 nm-1, respectively, ranging between 0.003 to 0.011 nm-1. Figure 3.5. Variability of 𝑎𝑁𝐴𝑃(𝜆) in all field trips (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝑁𝐴𝑃(𝜆) for each field trip. 3.3.6 Particle absorption The Figure 3.6 displays the spectral behavior of 𝑎𝑝 from 400 to 700 nm. It shows the contribution of phytoplankton and non-algal particle. Besides the magnitude, the shapes of 𝑎𝑝 from BB and Nav are clearly different, showing a smooth feature between 400 to 450 nm in Nav and a marked feature in BB. These are due to the high contribution of NAP and CDOM at this wavelength range, as also supported by Figure 3.1. On the contrary, BB was highly affected by photosynthetic pigments at the blue and red regions. The pattern from Nav was also observed by Meler et al. (2016) in Gulf of Gdánsk during winter and in river mouths, Baltic Sea during Rodrigues, T.W.P. 46 all seasons except summer. Wu et al. (2011) did not observe any feature at the blue and red regions due to high loads of inorganic sediment, which masked the phytoplankton contribution along the spectra. Figure 3.6. Variability of 𝑎𝑝(𝜆) in all field trips. (a) Nav1, (b) Nav2, (c) Nav3, (d) BB1, (e) BB2 and (f) the average value of 𝑎𝑝(𝜆) for each field trip. Different y axles were applied for Nav and BB due to magnitude discrepancies. 3.4. Discussion As reported in many studies, BB as the first reservoir of the cascade system receives high loads of sediments coming from the metropolit