From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river

Rivers play a key role in the global biogeochemical functioning, as they link the biogeochemical cycles of the terrestrial and oceanic systems. In the framework of the carbon cycle, streams and rivers receive dissolved organic matter (DOM) from a variety of sources which is subsequently transported...

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Author: Ejarque Gonzalez, Elisabet
Format: doctoral thesis
Status:Published version
Publication Date:2014
Country:España
Institution:CBUC, CESCA
Repository:TDR. Tesis Doctorales en Red
OAI Identifier:oai:www.tdx.cat:10803/286321
Online Access:http://hdl.handle.net/10803/286321
Access Level:Open access
Keyword:Contaminants orgànics de l'aigua
Contaminantes orgánicos en el agua
Organic water pollutants
Hidrologia
Hidrología
Hydrology
Biogeoquímica
Biogeochemistry
Ciències Experimentals i Matemàtiques
574
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oai_identifier_str oai:www.tdx.cat:10803/286321
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
title From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
spellingShingle From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
Ejarque Gonzalez, Elisabet
Contaminants orgànics de l'aigua
Contaminantes orgánicos en el agua
Organic water pollutants
Hidrologia
Hidrología
Hydrology
Biogeoquímica
Biogeochemistry
Ciències Experimentals i Matemàtiques
574
title_short From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
title_full From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
title_fullStr From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
title_full_unstemmed From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
title_sort From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean river
dc.creator.none.fl_str_mv Ejarque Gonzalez, Elisabet
author Ejarque Gonzalez, Elisabet
author_facet Ejarque Gonzalez, Elisabet
author_role author
dc.contributor.none.fl_str_mv Butturini, Andrea
Sabater i Comas, Francesc
Universitat de Barcelona. Departament d'Ecologia
dc.subject.none.fl_str_mv Contaminants orgànics de l'aigua
Contaminantes orgánicos en el agua
Organic water pollutants
Hidrologia
Hidrología
Hydrology
Biogeoquímica
Biogeochemistry
Ciències Experimentals i Matemàtiques
574
topic Contaminants orgànics de l'aigua
Contaminantes orgánicos en el agua
Organic water pollutants
Hidrologia
Hidrología
Hydrology
Biogeoquímica
Biogeochemistry
Ciències Experimentals i Matemàtiques
574
description Rivers play a key role in the global biogeochemical functioning, as they link the biogeochemical cycles of the terrestrial and oceanic systems. In the framework of the carbon cycle, streams and rivers receive dissolved organic matter (DOM) from a variety of sources which is subsequently transported downstream and delivered to the oceans. However, there is increasing evidence that this step involves not only a relocation of DOM from the land to the seas, but also an important in-stream processing which modifies its quality and properties and, to some extent, outgas it to the atmosphere as CO2. However, up to now it has not been assessed how these modifications occur along a longitudinal perspective and, most importantly, the role that hydrology plays in such downstream patterns of DOM processing. This thesis explores the transport and reactivity of DOM along a Mediterranean river (la Tordera) under a variety of hydrological conditions ranging from flash floods to summer droughts. First, the composition of DOM was determined using 3D fluorescence spectroscopy (emission-excitation matrices) and a novel chemometric approach based on a self-organising maps analysis coupled with a correlation analysis. This step allowed discerning the presence of four DOM moieties: a tyrosine-like, a tryptophan-like, and two humic-like fluorescence components. Next, longitudinal patterns of these components are presented for a range of hydrological conditions. Along the main stem, the river exhibited three reaches with a differentiated DOM character: in the headwaters DOM had an eminent humic-like character derived from the drainage of the surrounding terrestrial catchment (high HIX); in the middle reaches (from Sant Celoni to Fogars de la Selva) there was a predominance of the protein-like component C2 reflecting the effect of direct anthropogenic water inputs (concomitant high nutrient concentrations); and the lowest part of the river was dominated by the protein-like component C1 and high FI, suggesting a predominance of microbially-derived DOM. Hydrology appeared to act as a modulator of such longitudinal patterns: during drought, the spatial heterogeneity of DOM character was maximised, whereas during flood conditions there was an homogenisation over the longitudinal dimension, consisting in a highly aromatic humic-like character. By means of an End-Member Mixing Analysis (EMMA) approach it was observed that in-stream reactive processes were likely to be driving DOM quality, especially during non-flood conditions and at the middle and lower reaches of La Tordera. Following such evidences, the relevance of in-stream transformations over transport and physical mixing were explicitly quantified by performing a mass balance approach at thirteen consecutive downstream segments. Results of the mass balance study showed that flood events, despite their brevity in time, had the capacity to export the largest amounts of DOM, although having undergone little in-stream processing. During baseflow conditions, which have been estimated to occur annually about half of the days, there were moderate efficiencies of bulk DOM retention; however, individual fluorescence components had important in-stream generations, especially the protein-like moieties C1 and C2. In space, this processing occurred in the final segments of the river, hence exhibiting a shift from a conservative to a reactive behaviour. Finally, during drought conditions the river had the highest capacity of DOM retention and exported the least amounts of DOM. In space, retention efficiencies were homogeneous along the mainstem, except for two anthropogenically-impacted sites where the retention capacities were reduced. The mass balance study also revealed that bulk DOC processing was subject to a stoichiometric control with nitrate, even though such control was weaker during drought. The findings of this thesis demonstrate that the riverine passage is a decisive step that defines the quantity and quality of the DOM that is finally delivered to the oceans. Moreover, the observed hydrological seasonality in La Tordera shapes a temporally-changing DOM character which may have complex repercussions for its fate once in the coastal systems.
publishDate 2014
dc.date.none.fl_str_mv 2014
2015
2015
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
info:eu-repo/semantics/publishedVersion
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10803/286321
url http://hdl.handle.net/10803/286321
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv http://creativecommons.org/licenses/by/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 234 p.
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Universitat de Barcelona
publisher.none.fl_str_mv Universitat de Barcelona
dc.source.none.fl_str_mv TDX (Tesis Doctorals en Xarxa)
reponame:TDR. Tesis Doctorales en Red
instname:CBUC, CESCA
instname_str CBUC, CESCA
reponame_str TDR. Tesis Doctorales en Red
collection TDR. Tesis Doctorales en Red
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling From flood to drought: Transport and reactivity of dissolved organic matter along a Mediterranean riverEjarque Gonzalez, ElisabetContaminants orgànics de l'aiguaContaminantes orgánicos en el aguaOrganic water pollutantsHidrologiaHidrologíaHydrologyBiogeoquímicaBiogeochemistryCiències Experimentals i Matemàtiques574Rivers play a key role in the global biogeochemical functioning, as they link the biogeochemical cycles of the terrestrial and oceanic systems. In the framework of the carbon cycle, streams and rivers receive dissolved organic matter (DOM) from a variety of sources which is subsequently transported downstream and delivered to the oceans. However, there is increasing evidence that this step involves not only a relocation of DOM from the land to the seas, but also an important in-stream processing which modifies its quality and properties and, to some extent, outgas it to the atmosphere as CO2. However, up to now it has not been assessed how these modifications occur along a longitudinal perspective and, most importantly, the role that hydrology plays in such downstream patterns of DOM processing. This thesis explores the transport and reactivity of DOM along a Mediterranean river (la Tordera) under a variety of hydrological conditions ranging from flash floods to summer droughts. First, the composition of DOM was determined using 3D fluorescence spectroscopy (emission-excitation matrices) and a novel chemometric approach based on a self-organising maps analysis coupled with a correlation analysis. This step allowed discerning the presence of four DOM moieties: a tyrosine-like, a tryptophan-like, and two humic-like fluorescence components. Next, longitudinal patterns of these components are presented for a range of hydrological conditions. Along the main stem, the river exhibited three reaches with a differentiated DOM character: in the headwaters DOM had an eminent humic-like character derived from the drainage of the surrounding terrestrial catchment (high HIX); in the middle reaches (from Sant Celoni to Fogars de la Selva) there was a predominance of the protein-like component C2 reflecting the effect of direct anthropogenic water inputs (concomitant high nutrient concentrations); and the lowest part of the river was dominated by the protein-like component C1 and high FI, suggesting a predominance of microbially-derived DOM. Hydrology appeared to act as a modulator of such longitudinal patterns: during drought, the spatial heterogeneity of DOM character was maximised, whereas during flood conditions there was an homogenisation over the longitudinal dimension, consisting in a highly aromatic humic-like character. By means of an End-Member Mixing Analysis (EMMA) approach it was observed that in-stream reactive processes were likely to be driving DOM quality, especially during non-flood conditions and at the middle and lower reaches of La Tordera. Following such evidences, the relevance of in-stream transformations over transport and physical mixing were explicitly quantified by performing a mass balance approach at thirteen consecutive downstream segments. Results of the mass balance study showed that flood events, despite their brevity in time, had the capacity to export the largest amounts of DOM, although having undergone little in-stream processing. During baseflow conditions, which have been estimated to occur annually about half of the days, there were moderate efficiencies of bulk DOM retention; however, individual fluorescence components had important in-stream generations, especially the protein-like moieties C1 and C2. In space, this processing occurred in the final segments of the river, hence exhibiting a shift from a conservative to a reactive behaviour. Finally, during drought conditions the river had the highest capacity of DOM retention and exported the least amounts of DOM. In space, retention efficiencies were homogeneous along the mainstem, except for two anthropogenically-impacted sites where the retention capacities were reduced. The mass balance study also revealed that bulk DOC processing was subject to a stoichiometric control with nitrate, even though such control was weaker during drought. The findings of this thesis demonstrate that the riverine passage is a decisive step that defines the quantity and quality of the DOM that is finally delivered to the oceans. Moreover, the observed hydrological seasonality in La Tordera shapes a temporally-changing DOM character which may have complex repercussions for its fate once in the coastal systems.Els rius juguen un rol essencial en el funcionament biogeoquímic global, ja que enllacen els cicles biogeoquímics terrestres amb els oceànics. En el si del cicle del carboni, els rius reben matèria orgànica dissolta (MOD) d’una gran varietat d’orígens, la qual és transportada riu avall i alliberada al mar. Hi ha evidències creixents que aquest pas, no consisteix només en un transport conservatiu, sinó que a més, té lloc un processat intern que en modifica qualitats i, fins a cert punt, l’oxida i allibera a l’atmosfera en forma de CO2. Malgrat tot, fins ara no s’ha avaluat com ocorren aquestes modificacions des d’una perspectiva longitudinal, de capçalera a desembocadura, ni el rol que la hidrologia fluvial juga en el desenvolupament d’aquests patrons longitudinals. Aquesta tesi explora el transport i la reactivitat de la MOD al llarg d’un riu Mediterrani (la Tordera) durant un ventall de condicions hidrològiques que comprenen des de grans avingudes fins a sequeres estivals. Primerament, es presenta un nou mètode quimiomètric per a determinar la composició de la fracció fluorescent de la MOD basat en una anàlisi neuronal amb mapes autoorganitzats de Kohonen. Aquesta anàlisi revela la presència de 4 fraccions de matèria orgànica: una relacionada amb la tirosina, una amb el triptòfan, i dues amb substàncies húmiques. Seguidament, es presenten els patrons longitudinals d’aquestes quatre fraccions, juntament amb un balanç de masses calculat a tretze segments de riu situats consecutivament riu avall. Els resultats d’aquesta tesi doctoral demostren que el pas fluvial és un pas decisiu que determina la qualitat i la quantitat de MOD que és finalment alliberada als mars. Les crescudes, malgrat que són esdeveniments molt puntuals en el temps, representen la màxima capacitat del riu d’exportar MOD i, a més, ho fan amb un mínim processat intern. En canvi, durant cabal basal i sequera, tenen lloc importants canvis durant el transport fluvial. Aquesta estacionalitat temporal en la qualitat i quantitat de la MOD exportada, determinada principalment per les condicions hidrològiques, pot ser determinant pel destí que tindrà la MOD un cop al mar.Universitat de BarcelonaButturini, AndreaSabater i Comas, FrancescUniversitat de Barcelona. Departament d'Ecologia201520152014info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersion234 p.application/pdfapplication/pdfhttp://hdl.handle.net/10803/286321TDX (Tesis Doctorals en Xarxa)reponame:TDR. Tesis Doctorales en Redinstname:CBUC, CESCAInglésL'accés als continguts d'aquesta tesi queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons: http://creativecommons.org/licenses/by/3.0/es/http://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccessoai:www.tdx.cat:10803/2863212026-06-14T12:46:07Z
score 15,301603