Ph.D. Thesis

Author: Carme Barba Ferrer

Presenting: Xavier Sanchez-Vila

Barcelona, April 5th, 2019

Porous media as a canvas for hydro-bio-geo-chemical processes

Authors: Carme Barba-Ferrer, NúriaPerujo, Paula Rodriguez-Escales

A canvas view of a problem in porous media

2

Malevich, Museumof Modern Art, MOMA, New York City

In subsurface: One type of problem, difficult problem, not a single solution

Malevich, MOMA, NY

Mondrian, MOMA, NY

In subsurface: Looking at a combination of problems, somewhat isolated, all well-defined (clear boundaries)

4

Kandinsky, MOMA, NY

In subsurface: Looking at a combination of problems, all intertwined, so that if you remove one of them (one color) the painting becomes irrelevant rather than a masterpiece

So, the approach is a matter of taste, from looking at one side of the problem and getting as deep as possible, or else, at trying to see the multiple faces of porous media. The latter is our approach

General Introduction

5

Variables affecting performance of infiltration systems

Hydrological parameters

Water-sediment contact times

Availability of solutes in depth

Biogeochemical processes

BiocloggingSedimentgrain size

distribution

Water quality: Inorganic compounds, C-N-P cycles,

emerging organic compounds, bacterial pathogens, viruses, DNA

sequences,…

Site: Sant Vicenç MAR system

Llobregat River Basin

Low Valley Aquifer

• Sedimentation pond (5000 m2)

• Infiltration pond (6500 m2)

• Infiltration rate ≈ 1m/d

• Hydraulic conductivity ≈ 1000 m/d

PresenterPresentation NotesConstructed in 2009Many studies have been performed there (five PhD)

RESULTS: EC and T mapping

During recharge No recharge

• Defining different zones according to recharge influence

• Agreement with previous work (Valhondo 2017)

PresenterPresentation NotesD’aquí traiem: -zonificació (antecedents valhondo)- Fitting amb IDH

Malgrat estem en mesos molt diferents, les condicions de T i CE del background són constantsSi tinc temps, dibuixar profunditat dels piezòmetres

RESULTS: Intermediate Disturbance Hypothesis

Intermediate disruptions

promote microbial diversity

PresenterPresentation NotesPertobacions molt fortes, com són les de P8, ens baixen molt la diversitat, indicant que alguns m.o. tenen avantatge respecte dels altres i són dominants. Comentar amb XSV i AF IDH per a mostres del dry

RESULTS: Microbial communities in GW

Betaproteobacteriaand

Dehalococcoidia

Favored under recharge conditions

(indicators of different influence of recharge)

PresenterPresentation NotesThese plots contain a lot and dense information. I want to point out only some aspects. As I told you before, each colour is a microbial class. The species belonging to each class were also known but we put this graph as a simplificationWe found a more or less defined pattern for each water type during wet period. The presence of B, Cyano and bacilli and Gamma for TIII, the presnsce of B, cyano, bacilli, Dehalo, Acido, Actino, Nitro in TIV or also a similar patter for the two samples of TII. However, dry samples did not follow any logical pattern between them.For instance, Betas and Dehalos grew more under recharge conditions. The main species found in P8 is Vogesella indigofera (catabolization of monosaccharides under high oxygen concentrations, but also can do denitrification. This allow to think that is a versatile microorganism, adapting their metabolism depending on the environmental conditions. Furhtermore, P8 is under the pond, and it is probably the most changing conditions point there. It is confirmed that denitrification occurs there (thanks to isotopic studies). Dehaloccocoides is represented by Dehalogenimonas sp. Some strains of this species are dechlorinators. This genus is strictly anaerobic. We can explain their presence here by the existence of microsites (local anoxic areas that coexist with fast-traveling oxygen-rich paths. In fact, TCA is a pollutant traditionally reported in the Llobregat River Valley at high levels. This is an hypothesis that can indicate the presence of this specie there and specially when anaerobic microsites are promoted due the reactive layer and recharge. Més unknow en el dry. De fet,es van sequenciar les més dominants. Aquestes es trobaven al wet. Per tant, les grises del dry corresponen a poblacions menys abundants (cosa que ja reflectia l’index d’equitativitat, més alt per al dry en promig. En el cas del P8 l’espècie predominant de Betes és methylotenera mobilis, desnirtifiant. Encara hi ha DN malgrat la recàrrega està parade (also reported in Grau-M 2018).Per tant, el que ens indiquen aquests 2 gràfics és que en el wet tenim poblacions dominants, molt probablement afavorides per la càrrega orgànica que porta l’aigua de recàrrega I especialitzades a degrader-la. (Tal I com exemplifica el P8). The same analyses were done for soil samples and surface water in wet period. But???

Principal Component Analysis on water samples

Recharge conditions

No recharge

• Separation of samples for operational period

• EC α Cu-log, Na, Cl• Shannon & Richness 1/ α

Betapr.

24 variables:2 componentsexplain 75% of the total variance

Hydrochemi-cal (major, minor ions, trace), field parameters

Relative abundances (classes & species)

WATER SAMPLES (21 samples)Grain-

size distrib.

parameters

Diversity indices

Depth

SOIL SAMPLES (10 samples)

Recharge/No

recharge

A LAB EXPERIMENTChapter I. Interaction between physical heterogeneity and microbial processes

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Dissolved nutrients, DOC, DOM quality indexes and DO

Interstitial DO

Bacterial density, bacterial viability, algal biomass, EPS, extracellular enzyme

activities (EEAs), functional diversity

Hydraulic Conductivity (K)

Dissolved nutrients, DOC, DOM quality indices, DO and

BDOC

Total duration: 33 daysConstant temperature: 20 ºCEverything in triplicate

Chapter I. Interaction between physical heterogeneity and microbial processes

12

Results & Discussion

Time (days)0 5 10 15 20 25 30 35

K/Ko

0,0

0,4

0,8

1,2

1,6CoarseFine - CoarseFineCoarse - FineMixture

1.2

0.8

0.4

0.0

1.6

K (m·day-1)Advection time

(seconds)Coarse 0.31b ± 0.11 736a ± 700

Fine – coarse 0.10a ± 0.06 3890c ± 2313

Fine 0.13a ± 0.05 2500bc ± 1482

Coarse – fine 0.19ab ± 0.11 1577ab ± 1160

Mixture 0.11a ± 0.03 2029ab ± 1231

N-NH4+

(µg N·L-1·s-1)

N-NOx(µg N·L-1·s-1)

P-PO4-3

(µg P·L-1·s-1)

Coarse -1.70b ± 1.17 2.14b ± 1.61 0.001a ± 0.04

Fine-coarse -0.36a ± 0.10 0.22a ± 0.29 -0.018b ± 0.02

Fine -0.52a ± 0.23 0.38a ± 0.29 -0.023b ± 0.03

Coarse-fine -0.75a ± 0.43 0.63a ± 0.73 -0.014b ± 0.01

Mixture -0.49a ± 0.15 0.49a ± 0.19 -0.012b ± 0.01

Nutrient balances (outlet – inlet)

higher transfer ofnutrients, organicmatter and DO indepth

Higher K

Higher process rates

BUT no phosphorous removal

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Results & Discussion

Higher bacterial density at 40 cm depth

Higher algal biomass

Higher biomass in the interface

Lowest value offunctional diversity indepth

In the coarse treatmentLive/Dead ratio decreasedin depth.

Extracellular enzymes

AlgaeBacteria

Chapter I. Interaction between physical heterogeneity and microbial processes

14

P balance FINE, FINE-COARSE and MIXTURE:

Low hydraulicconductivity favoredprocesses such as algalgrowth, P uptake by algaeand P adsorption

COARSE:High hydraulicconductivity coincides withno P removal as well aslow proportion of livebacteria and lowfunctional diversity

COARSE-FINE: The interface in the coarse-fine treatment promotes theaccumulation of biomassand enzyme activitiescreating hot-spots ofbacterial activity

Lapworth et al. (2012). EP.

Sorption and degradation (mainly by co-metabolism) are two of the most importantprocesses affecting the fate of UV-filters.

UV filters are used as personal and care products like sunscreens and cosmetics(perfumes, creams or shampoos), and in a number of industrial applications

Some of them are endrocrinedisruptors and have estrogenic activity

Effect of redox conditions and influence of biomass adsorption in UltraViolet-filter’s fate

Sorption also has been treated as a “phenomenological” process.

Benzophenone-3(w)

SedimentaryOrganicMatter

Benzophenone-3(s)IT IS NOT AS SIMPLE…

Most of current models of degradation of EOCs only focus on apparent processes

C kCt

∂= −

∂ 1/2lnKT2

=

What is solid organic matter in an aquifer?

Sedimentary organic matter- It is the traditional SOM (0.01-0.1)- Normally, it is recalcitrant.

Biomass- Not important if aquifers are not biologically active- Biomass can be an important sorbent biofilmformation (e.g. during Managed Aquifer Recharge, bioremediation…)

Test it with data from batch experiments (Liu et al., 2013) evaluating the fate of a cocktail of UV-filters in different redox conditions.

CONCEPTUAL MODEL

OCsed

OClab

BM CO2

EAUV-filter (s) UV-filter (l)

TP1

2

3

4

1

2

3

4

UV-filter sorption

Hydrolisis of OCsed

Oxidation of labile OC and growth of biomass

Co-metabolic degradation of UV-filters

3.1 3.2

OCsed Sedimentary organic carbonOClab Labile organic carbónTP Transformation productEA Electron AcceptorBM Biomass

1

UV-filter’s fate depends onbiogeochemical processes

Coupling sorption and degradation of UV filters with

geochemical models

RESULTS

• UV-filters mass is fitted but there is a problema in Kd…

• It seems we miss some process…

• We hypothesized that an intermediate surfaceappear from initial SOM

Biomass surface SOM surface

Modeling results: evolutoin of UV filters in water and solid surfaces

RESULTSEffect of redox conditions in fate’s processes of UVs- filter

Conclusions

• Life is difficult because it is non-linear

• Flow and transport in porous media are difficult to understand because there are a myriad of processes taking place simultaneously that are correlated

• We are still learning about them, and hope we will be doing that until infinity … and beyond

PresenterPresentation NotesDehalogenation give us an idea of potential bioremediation actions.

�Porous media as a canvas for hydro-bio-geo-chemical processesA canvas view of a problem in porous mediaSlide Number 3Slide Number 4General IntroductionSlide Number 6Slide Number 7Slide Number 8Slide Number 9Slide Number 10Chapter I. Interaction between physical heterogeneity and microbial processesChapter I. Interaction between physical heterogeneity and microbial processesSlide Number 13Chapter I. Interaction between physical heterogeneity and microbial processesEffect of redox conditions and influence of biomass adsorption in UltraViolet-filter’s fateSlide Number 16Slide Number 17Slide Number 18Slide Number 19Slide Number 20Slide Number 21