Articulo CQD

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Applied Chemistry
Easy and Rapid Synthesis of Carbon Quantum Dots from Mortiño
(Vaccinium Meridionale Swartz) Extract for use as Green Tracers in
the Oil and Gas Industry: Lab-to-Field Trial Development in Colombia
Carlos A Franco, Carlos H. Candela, Jaime Gallego, Jhon F. Marin, Luis E. Patiño, Natalia Ospina, Edgar
Patiño, Mario Molano, Fabio Villamil, Karla Bernal, Sergio Lopera, Camilo A. Franco, and Farid B. Cortés
Ind. Eng. Chem. Res., Just Accepted Manuscript • Publication Date (Web): 29 May 2020
Downloaded from pubs.acs.org on May 29, 2020
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Page 1 of 30 Industrial & Engineering Chemistry Research
1
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3 1 Easy and Rapid Synthesis of Carbon Quantum Dots from Mortiño (Vaccinium
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2 Meridionale Swartz) Extract for use as Green Tracers in the Oil and Gas Industry:
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8 3 Lab-to-Field Trial Development in Colombia.
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11 4 Carlos A. Franco1, Carlos H. Candela1, Jaime Gallego2,3,*, Jhon Marin2, Luis E.
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5 Patiño2, Natalia Ospina4, Edgar Patiño4, Mario Molano1, Fabio Villamil1, Karla M.
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16 6 Bernal1, Sergio H. Lopera5, Camilo A. Franco2,*, and Farid B. Cortés2,*
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18 1
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7 Ecopetrol S.A., Gerencia de Desarrollo Sur, Neiva, Huila, 410010, Colombia.
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8 2 Grupo de Investigación en Fenómenos de Superficie – Michael Polanyi, Facultad de
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23 9 Minas, Universidad Nacional de Colombia Sede Medellín, Kr 80 No. 65-223, Medellín,
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10 Antioquia, 050034, Colombia.
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11 3 Química de Recursos Energéticos y Medio Ambiente, Instituto de Química, Universidad
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30 12 de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Antioquia, 050010, Colombia.
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32 13 4 Petroingeniería de Antioquia- Petroraza SAS, Calle 80sur No. 47D-16, Sabaneta,
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35 14 Antioquia, 055450, Colombia.
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37 15 5 Grupo de Investigación de Yacimientos de Hidrocarburos, Facultad de Minas,
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39 16 Universidad Nacional de Colombia Sede Medellín, Kr 80 No. 65-223, Medellín,
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17 Antioquia, 050034, Colombia.
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44 18
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46 19 * Corresponding authors: andres.gallego@udea.edu.co; caafrancoar@unal.edu.co;
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20 fbcortes@unal.edu.co.
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51 21
52
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54 22 Abstract
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57 23 The main objective of this study is to develop nanotechnology-based materials, specifically
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60 24 carbon quantum dots (CQDs), as alternative non-polluting, non-toxic, and easily
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Industrial & Engineering Chemistry Research Page 2 of 30
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3 25 manipulated tracers for the oil industry using an easy and rapid synthesis from Mortiño
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26 (Vaccinium meridionale Swartz) extract, a process which was evaluated in the laboratory
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8 27 and subjected to a Colombian oil field trial. The CQDs were synthesized using an easy and
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10 28 rapid microwave-assisted carbonization (MWC) methodology involving aqueous natural
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29 extraction in the presence of an organic nitrogen precursor. A displacement test at reservoir
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15 30 conditions in a porous media was used for evaluating CQDs retention, and a breakthrough
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17 31 curve with a CQDs saturation of around 1 pore volume injected was obtained, indicating
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19 32 that the CQDs could be completely removed from the porous media with null retention due
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22 33 to a poor interaction with the formation and preferential affinity to the aqueous phase.
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24 34 Fluorescence tests showed that quantification of the synthesized CQDs could be achieved
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26 35 for up to 1 ng∙L-1. Coreflooding tests at reservoir conditions were performed under two
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36 scenarios: 1) monophase coreflooding (the core was saturated with water), and 2) biphasic
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31 37 coreflooding (at residual saturation of crude oil). The results showed that the CQDS behave
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33 38 excellently within these outlines and are not affected by the presence of crude oil, obtaining
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39 a breakthrough that is almost ideal for a tracer. A CQDs field trial in Colombia was
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38 40 conducted by injecting 20 kg of the nanomaterial at a concentration of 500 000 mg∙L-1. The
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40 41 CQDs were analyzed in 10 producer wells, showing that they are useful as inter-well tracers
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42 42 and the different interconnections between the different wells in the field were stablished.
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45 43 This study places the technology at a technology readiness level (TRL) of around 8, opens
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47 44 a broader landscape for the use of nanotechnology in the oil industry and maintains
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49 45 Colombia as a pioneer in the application of nanoparticles and nanofluids under field
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46 conditions.
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55 47 Keywords: Carbon quantum dots; Mortiño (Vaccinium meridionale Swartz); extract; crude
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57 48 oil; tracers; coreflooding test; field trial.
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60 49
50

1
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3 51 1. Introduction
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6 52 A tracer is a substance introduced into a system, i.e., a biological, geological, or other
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8 53 system, so that its subsequent distribution may be followed readily based on its properties,
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11 54 such as its color, radioactivity and chemical nature, among others. In general, tracers are
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13 55 divided into two groups: i) radioactive and ii) non-radioactive compounds,1 which have been
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15 56 used in a wide variety of applications. However, these materials have various limitations for
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17
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57 their use due to their toxicity, transport and manipulation restrictions, high costs and logistics
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20 58 related to analytical quantification and analysis, and feedback.1
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22 59 In particular, the oil and gas industry reported the use of tracers in the ’50s for tracking
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60 the flow of fluids in water-flooded reservoirs. Tracers were added to the injected fluids to
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27 61 determine where the fluids were going.2 Due to the heterogeneity of the reservoirs, fluid
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29 62 movement is challenging to predict, especially in fields that contain multiple injectors and
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31 63 producers.3 However, the flow path can be identified by tagging fluids at each injection well
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33
34 64 with different tracers and the further monitoring of the tracers appearing at each producing
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36 65 well.4
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38 66 A wide range of chemical compounds has been used as tracers, depending on the aim
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67 and their specific characteristics.5 For inter-well tracers involved in water injection, it is
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43 68 desirable for the chemical compound to not interact with the mineral formation and have a
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45 69 low solubility in the oil phase. Another important topic related to tracers is the analysis and
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70 analytical methods used after the injection. Tritiated water is the most frequently used
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50 71 radioactive tracer. Its properties are very similar to those of regular water; therefore, it does
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52 72 not disturb the chemical equilibrium of most subsurface reservoirs.6 Also, radioactivity is a
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54 73 very sensitive property that can be measured very precisely. Thus, a wide variety of
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57 74 radioactive chemical compounds have been used as tracers in the oil industry. Most of them
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59 75 are related to tritiated compounds and the others based on radioactive isotopes of metal
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76 cations, such as Eu-154, Cs-134, Cs-137, Co-57 and Co-60, among others.1 However,

1
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3 77 radioactive compounds have intrinsic issues related to their exposure, transport,
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78 instrumentation for analysis and costs, among others.7 In the last decades, non-radioactive
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8 79 chemical compounds have gained relevance as tracers due to their vast variety, lower toxicity,
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10 80 economical application and facility in terms of production or acquisition versus radioactive
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81 tracers. Nevertheless, they have also some issues as high concentrations are needed, i.e., due
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15 82 to their analytical procedures they have certain interactions with the mineral formation or
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17 83 partition to the oil phase.2 At present, fluoribenzoic acid derivates (FBA) are the most used
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19 84 inter-well tracers in the oil industry.8 However, these compounds have been reported to be
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22 85 recalcitrant and toxic for humans and animals.9 Therefore, with the aim to reduce the quantity
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24 86 of these tracers needed, highly accurate analytical-instrumental techniques have been
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26 87 developed around these applications that are now able to quantify parts per trillion (ppt –
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88 ng∙L-1).5 It should be noted that all this technification carried with it an augmentation of the
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31 89 analytical costs and a significant time delay between the sampling and the final results,
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33 90 leading, sometimes, to poor decisions being made in oil fields.
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35
91 With the development and industrialization of nanotechnology, all the petrochemical
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38 92 processes have been improved, i.e., extraction, refinement, and consumption.10 In that
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40 93 direction, it is possible to find some recent reports relate to the use of nanoparticles as tracers
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42 94 in the oil industry. Fluorescent materials are excellent candidates as tracers due to their
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45 95 excellent quantification limits; in some cases, this limit is nearly nanograms per liter (ppt,
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47 96 ng∙L-1). To the best of our knowledge, oil and gas companies are evaluating nanoparticles,
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49 97 such as carbon quantum dots (carbogenic nanoparticles; CQDs) and fluorescent
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51
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98 functionalized nano-silica, as tracers for the oil and gas industry. Kosynkin et al.,11 report
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54 99 carbogenic nanoparticles, named “A-Dots”, were evaluated in a huff-n-puff process and
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56 100 exhibited a recovery close to 85%. Based on these results, the authors concluded that these
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101 types of nanoparticles have a tracer behavior and can be used for understanding inter-well
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102 fluid dynamics. Murugesan et al.12 reported on CQDs synthesized using an electrochemical

1
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3 103 reaction. These CQDs showed different colors under UV irradiation, depending on the
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104 nitrogen content in their structures. The authors tested, in a lab-scale sand-packed montage,
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8 105 the retention of the CQDs in the porous formation, producing a breakthrough of around one
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10 106 pore volume with 75% recuperation after 7.5 pore volumes. This fact shows how these CQDs
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107 have some retention in the porous media, which is not desirable in a tracer. Elis et al. (Saudi
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15 108 Aramco Company) evaluated the use of CQDs as a tracer during waterflood oil recovery.
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17 109 However, they used a thermal carbonization methodology to obtain the CQDs and evaluated
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19 110 them in a field-scale test. They compared their CQDs with other two commercial tracers,
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22 111 showing that CQDs’ performance is related to the percentage of recuperation after oil
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24 112 production. Until now, only one evaluation of field test has been performed, which was done
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26 113 by Alaskar et al.13 in a carbonate reservoir.
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114 Quantum dots (QD) are nano or sub-nanometric materials which exhibit the particular
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31 115 property of electron quantum confinement, due to the resonance between the electron
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33 116 wavelength and particle size, which provides some particularities, such as fluoresce with a
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117 high quantum yield.14 Originally, QD were made from heavy transition elements, such as
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38 118 ZnS and CdSe, among others, and were semiconductors. Recently, as mentioned above,
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40 119 quantum dots made from carbonanceous materials (CQD) have also been prepared and
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42 120 characterized with different aims.14 The principal advantages of CQDs compared to heavy-
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45 121 transition-element-based QD are that they have a wide range of carbonaceous precursors,
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47 122 including bio-resources and residues, CQDs are reported to be non-toxic and there are many
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49 123 processes through which they can be obtained, including top-down and bottom-up, as well
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124 as various other methodologies. Varying these conditions results in different CQDs
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54 125 properties, such size, chemical composition, impling that diffetent optical response
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56 126 (“colors”) when irradiated with UV light.. The bottom-up process used to obtain CQDs is
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127 commonly referred to as carbonization. This process often includes solvo-thermal treatment,
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128 with water being the most common solvent (a hydrothermal process in this case). In addition,

1
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3 129 thermal carbonization in different atmospheres, chemical reduction and oxidation using
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130 different agents, and assisted carbonizations via microwave, ultrasound, and plasma-
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8 131 assistance have been used.14 On the other hand, a broad array of carbonaceous precursors
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10 132 have been reported, such as pure chemicals, organic residues, plant extracts, and so on.
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133 The final application of the CQDs must be taken into account, meaning that the purity
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15 134 and traceability of the process must be considered. Microwave-assisted synthesis has been
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17 135 reported as a rapid, simple, and cost-effective methodology for the chemical synthesis and
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19 136 processing of nanomaterials, including CQDs.15
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22 137 Even if CQDs are being implemented as tracers in the oil and gas industry,11, 13, 16-19 there
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24 138 are no reports, to the best of our knowledge, of CQDs being produced using a domestic
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26 139 microwave oven and Mortiño (Vaccinium Meridionale Swartz) extract, then used as green
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140 tracers. As mentioned above, CQDs are potential tracers for the oil industry. However, there
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31 141 is scant information about their chemical composition, interactions with the different
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33 142 components during oil production as well as other essential factors. Furthermore, production
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143 of tropical fruits extracts may result in commercialization issues, as the residue cannot be
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38 144 exported or consumed. In this order, the use of the fruit-derived residue can lead to additional
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40 145 exploitation as a cost-effective way to produce CQDs. This synthesis method and the non-
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42 146 pure reagent, for example a natural extract, lead to a non-toxic material with a variety of the
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45 147 organic functionalities that guarantee high stability in the injection fluid, more effective
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47 148 interaction with the aqueous systems, and high sensitivity for on-site measurement, which
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49 149 results in lower cost associated with the operation and lower time of traceability analysis.13
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150 Hence, the main objective of this study is to investigate the microwave-assisted synthesis
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54 151 of CQDs using Mortiño (Vaccinium Meridionale Swartz) extract in terms of ease, scalability,
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56 152 and economical use under laboratory conditions and via a field trial in a Colombian
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153 reservoir. It is worth to mention that the main advantages of this study are related to the
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154 developed material based on the easy preparation and detection, as well as the first field

1
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3 155 application as inter-well tracers in a sandstone reservoir, which certainly opens a wider
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156 landscape about the use of nanotech-based green solutions for enhanced oil recovery.
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8 157
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10 158 2. Materials and Methods
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159 2.1. Materials
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16 160 Mortiño (Vaccinium Meridionale Swartz) has a high potential for commercialization due
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161 mainly to its high nutritional value and antioxidant potential.20 The fruit is a berry with a
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21 162 diameter of 5 mm–10 mm which is red-to-black when it is ripe. However, there has been no
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23 163 research on its industrial potential in terms of obtaining carbogenic nanoparticles from its
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164 rich extract of citric acid.
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28 165 Mortiño was purchased in a market located in El Retiro, Antioquia, Colombia in
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30 166 adequate physical condition and a degree ripeness consistent with a mass fraction of citric
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32 167 acid of 1.5% and moisture of 83.5%. The fruit was washed with a chlorine solution (100
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35 168 mg∙L-1) to remove any dirt, cut posteriorly and squeezed to obtain the juice extract. Next, the
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37 169 extract was filtered using Whatman filter paper and concentrated using a domestic microwave
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39 170 oven at 200 W for 15 min until an adequate concentration was reached (approximately 4 M
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171 of natural citric acid). Ethylenediamine (C2H8N2) with a purity of 99% (PanReac) was used
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44 172 as a nitrogen donor. The concentration of the extract and the carbonization were done using
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46 173 a domestic microwave oven (Haceb 0.7 AR HM) with variable power ranging between 1000
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48
174 W and 100 W.
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51 175 The dynamic tests were conducted in two stages, i.e., one stage at atmospheric conditions
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53 176 and another stage at high pressure and temperature. For the first stage, Ottawa sand with a
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55 177 mesh of 30-70 was used. A 30-cm-long, 3-cm-in-diameter glass tube with a passage valve,
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58 178 class E glass fiber for sand support, flow line and a positive displacement pump was used.
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60 179 For the second stage, a core from a Colombian field (CF) was employed. The porous media

1
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3 180 had an absolute permeability of 56 mD, porosity of 19%, diameter of 3.82 cm and length of
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181 7.91 cm. Crude oil of 21.6 °API with a kinematic viscosity of 118.17 mm2∙s-1 and a mass
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8 182 fraction for the asphaltene content of approximately 13% was used. A positive pump,
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10 183 manifolds, valves and a core holder rounded out the equipment.21 Injection brine from the
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184 field of interest was used for experiments and some properties are summarized in Table 1.
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15 185 Table 1. Properties of the injection brine of the Colombian field of interest.
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17 Property Value
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19 Na+ (mg∙L-1) 226
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21 K+ (mg∙L-1) 4.6
22 4.3
Ca++ (mg∙L-1)
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24 Mg++ (mg∙L-1) 0.4
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26 Ba++ (mg∙L-1) < 0.55
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28 Sr++ (mg∙L-1) < 0.13
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Fe++ (mg∙L-1) 0.1
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31 HCO3- (mg∙L-1) 275
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33 CO3= (mg∙L-1) 15.0
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35 SO3= (mg∙L-1) 5.0
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Salinity (NaCl mg∙L-1) 542
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38 Density (g∙mL-1) 0.999
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40 Turbidity (NTU) 3.0
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42 186
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45 187 2.2. Methods
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48 188 2.2.1. Synthesis of the carbon quantum dots
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51 189 The CQDs were synthesized via a microwave-assisted carbonization methodology,
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190 adapted from the one reported by Pham.22 A concentrated aqueous Mortiño extract, at around
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56 191 4 M of citric acid, was homogenized for 20 min using a magnetic stirrer for 20 min. Next, in
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58 192 a 10 mL glass test tube, 0.5 mL of pure ethylenediamine (N-donor) was added to 2 mL of the
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60 193 concentrated natural extract. It is important that this step be done in the correct order and

1
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3 194 slowly due to the exothermicity of the dissolution and reactions of the reagents. This mixture
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195 was then stirred magnetically for 30 s, obtaining a browned, homogeneous solution. The
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8 196 mixture was irradiated using a domestic microwave oven for 6 min at 300 W. After this step,
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10 197 a hot, browned, gel-like solution was obtained. This gel-like solution was dissolved (or
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198 dispersed) using a water bath of 5 mL of distilled water at around 80 ℃, resulting in a yellow-
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15 199 browned dispersion. Finally, a Whatman filter was used to filter the solution to remove CQDs
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17 200 the solids from the natural extract. Figure S1 shows the appearance of the materials during
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201 the different preparation steps.
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23 202 2.2.2. Characterization of the CQDs
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203 The physicochemical properties of the synthesized nanomaterials were characterized
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28 204 through High-resolution transmission electron microscopy (HR-TEM), thermogravimetric
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30 205 analyses (TGA), atomic force microscopy (AFM), Fourier transform infrared spectroscopy
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206 (FTIR), X-ray photoelectron spectroscopy (XPS), zeta potential and dynamic light scattering
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35 207 (DLS) following the procedures described in previous publications.23, 24 Additionally, the
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37 208 CQDs were characterized using a LS-55 Fluorescence Spectrometer (Perkin Elmer, USA)
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39 209 equipped with a Xenon lamp and a Monk-Gillieson-type monochromator. For the analysis, 1
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42 210 cm of an optical cross-section quartz cuvette was used.
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44 211 The interfacial tension (IFT) between crude oil-water and crude oil–nanofluid was
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46 212 evaluated to identify any possible interactions between the CQDs and the reservoir fluids.
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213 IFT measurements were performed at 25 ℃ via the Wilhelmy plate method using a force
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51 214 tensiometer – K11 (Krüss, Germany). All experiments were repeated three times with a
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53 215 standard deviation of approximately 5% and an accuracy of 0.001 mN∙m-1.
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216 2.2.3. Compatibility tests
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59 217 Compatibility tests were performed between crude oil and a CQDs dispersion of 100
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218 mg∙L-1 in the injection brine. These tests are of primary importance to check for possible

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3 219 generation of an undesirable third phase, or undesirable emulsification in the oil or water
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220 phase. Three different volumetric relations were added to a hermetic test tube, i.e., 20/80,
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8 221 50/50 and 80/20 CQDs dispersed in brine/crude oil, for a total volume of 10 mL. The mixes
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10 222 were subjected to vigorous manual agitation for 30 s, then the systems rested at 57 °C
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223 (reservoir temperature) for 2 hours. After this time period, the system was analyzed visually
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15 224 to see if an emulsion or other phases had formed. An aliquot was taken from the aqueous
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17 225 phase to measure the photonic response, more specifically, the florescence.
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20 226 2.2.4. Retention of CQDs at the micro-lab-scale under atmospheric conditions
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23 227 A micro-lab-scale porous media was used to evaluate the retention of the CQDs. Ottawa
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228 sand with a mesh of 30 -70 was washed with distilled water and dried at 50 ℃ overnight.
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28 229 Then the sand was packed in a 30-cm-long and 3-cm-diameter glass tube with glass fiber
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30 230 beds at the bottom and top of the tube to avoid the sand particles being dragged by the fluid
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231 flow and pressure. At the external bottom of the tube, 1/8-inch tubing connected the sand
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35 232 pack to a syringe pump. Similar tubing was connected at the top to facilitate sample
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37 233 collection. Using the porous set-up (Ottawa sand pack) vertically, a distilled water flow of 1
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39 234 mL∙min-1 was passed through the system until four pore volumes was reached in order to
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42 235 reach complete saturation of the porous media. After that, 100 mg∙L-1 of CQDs dispersed in
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44 236 water was injected into the porous media at a volumetric flow of 1 mL∙min-1 until four pore
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46 237 volumes was reached. Next, the porous media was cleaned using three pore volumes of
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238 distilled water. During all injection processes, samples of 4 mL were collected and analyzed
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51 239 using a fluorometer. However, this type of test must be corroborated at reservoir conditions
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53 240 to provide excellent flow assurance and avoid any formation damage in the field.
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241
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58 242
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60

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3 243 2.2.5. Retention of CQDs – coreflooding under high pressure and temperature
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244 reservoir conditions
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8 245 For the displacement tests, a core from a Colombian field was used at reservoir
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11 246 conditions of a temperature of 57 °C, pore pressure of 1200 psi and overburden pressure of
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13 247 2000 psi. These are considered to be the basic petrophysical properties of the porous medium
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15 248 and allow the construction of the retention curves at 100% brine saturation and residual oil
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17
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249 saturation Sor. Washing with toluene and methanol was carried out once the first stage of each
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20 250 test was completed in order to guarantee the same conditions for the two scenarios. The
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22 251 procedure started with the injection of 5 pore volumes (PV) of production brine.
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252 Subsequently, 3 PV of CQDs tracer was injected at 100 mg∙L-1 diluted in the injection water.
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27 253 At this point, the retention curve began collecting the effluents every 2 mL and measuring
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29 254 their fluorescence in the Perkin Elmer Fluorometer, as described above. Finally, 3 PV of
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31 255 injection water was injected again to displace the tracer and complete the retention curve of
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34 256 the CQDs.
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36 257 The second stage involving residual oil saturation consisted of first conditioning the core
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38 258 at optimum conditions for displacement. Then came the injection of 5 PV of production brine.
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259 Afterwards, 5 PV of oil was injected to saturate the medium to the point of irreducible water
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43 260 saturation. Subsequently, injection brine was injected until residual oil saturation was
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45 261 reached. Finally, the steps for the injection of the tracer in the previous condition were
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262 repeated with 100% brine saturation. In addition, oil recovery curves were obtained through
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50 263 the injection of the CQDs at different concentrations for flow-assurance and to corroborate
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52 264 that there is no addition interaction of CQDs with the porous medium and the reservoir fluids.
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54 265 The above-mentioned assembly is detailed in Figure 1.
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56
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58
59
60

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266
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18 267 Figure 1. Experimental set-up for the Colombian field condition displacement
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20 268 using a real core.
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24 269 2.2.6. Field application
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270 The Colombian field of interest is located in the south of Colombia and has a daily
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29 271 injection of approximately 10 000 barrels of water per day. Prior to the injection of the tracer,
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31 272 injection and production water blanks were taken. Then 20 kg of CQDs at a mass fraction of
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33 273 50% (500 000 mg∙L-1) was injected. Afterwards, samples were taken at the head of nine
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36 274 producer wells two times per day. Next, the samples were taken to the laboratory of the field,
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38 275 and fluorescence was used to detect the presence of CQDs.
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40 276 The injector well has had a water injection process since August 2018, with an average
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42
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277 flow of 600 BWPD. The producing wells in the pattern are located a distance that varies
44
45 278 between approximately 150 m and 750 m. During the injection time prior to injection of the
46
47 279 CQDs, no conventional tracers had been run. It is important to mention that as a peculiarity
48
49
280 of this field, the distribution of the production formation channels and the connectivity
50
51
52 281 between wells provided available injection/production data to assess the accuracy of the
53
54 282 CQDs. Hence, prior to the CQDs, the field geologist was carrying out a reinterpretation of
55
56 283 the model, to generate the channel geometries of this formation and to evaluate the
57
58
59 284 connectivity of the wells.
60

1
2
3 285 3. Results and Discussion
4
5
6
7
286 3.1. Characterization of CQDs
8
9 287 The synthesized quantum dots were obtained from Mortiño (Vaccinium Meridionale
10
11
12 288 Swartz) extract and had a yield of about 80% regarding organic content of the precursor
13
14 289 solution. It is worth to mention that the fruit can be obtained from those lots that are not
15
16 290 adequate for export or human consumption, which lead to a cost-effective way to produce
17
18
19
291 CQDs and valorization of this product. One of the main characteristics of the quantum dots
20
21 292 is surface electronic quantum confinement, which is expressed as luminescence. As shown
22
23 293 in Figure S1, the prepared material shows fluorescence when it is irradiated with a UV light
24
25
294 (360 nm). In this case, a common UV lamp was used as a qualitative test. Figure 2a shows
26
27
28 295 the photonic response of the as-prepared CQDs, with absorbance and fluorescence noted at
29
30 296 10 mg∙L-1. In this figure, it is possible to see that the CQDs show a well-defined spectrum
31
32 297 with a broad fluorescence signal centered at 453 nm excited at 350 nm. These wavelengths
33
34
35 298 are common for carbonaceous quantum dots with oxygenated and nitrogenated functional
36
37 299 groups. Mugressan et al. 18 showed how the presence of nitrogen in N-doped CQDs generates
38
39 300 a blue shift in the fluorescence wavelength. Hence, it is possible to change the color, or the
40
41
42
301 fluorescence wavelength, by changing the chemical composition or introducing dopants.
43
44 302 These organic functional groups containing heteroatoms, such as O, N, and S, generate a
45
46 303 dipolar moment from the center to the border of the CQDs, which attract the electrons once
47
48
304 excited under UV light. This effect generates a concentration of the electrons around the
49
50
51 305 nanoparticles or CQD, which is responsible of the fluorescence phenomena, due to a loss of
52
53 306 energy, when the electrons are coming back to its original site. This fact, suggest that
54
55 307 modifying the quantity and nature of the organic functionalities on the CQDs, it is possible
56
57
58 308 to modulate its optical response, or its fluorescence wavelength (“colours”).
59
60

1
2
3 309 Different concentrations of CQDs in aqueous dispersion were prepared via simple
4
5
6
310 mixing using the as-prepared gel or a mother solution (at around 100 000 mg∙L-1). Figure 2b
7
8 311 Absorbance calibration curve, fluorescence calibration curve at 1% of detector attenuance,
9
10 312 and fluorescence calibration curve without attenuance. In this figure, it is possible to see an
11
12
313 excellent linear correlation between the photonic response and concentration, which is
13
14
15 314 present between 1 ng∙L-1 (through fluorescence) until 400 mg∙L-1 (through absorbance). Thus,
16
17 315 photonic spectroscopy, i.e., UV-Vis absorbance and fluorescence, makes it possible to
18
19
316 measure a wide range of CQDs concentrations with in-opperando and/or in-situ
20
21
22 317 characterizations and quantifications.
23
24 a)
25
26
27
28
29
30
31
32
33
34
35
36
37
b)
38
39
40
41
42
43
44
45
46
47
48
49
50 318 Figure 2. a) 3-D fluorescence spectrum as a function of the excitation wavelength
51
52 319 (left), and the absorption and fluorescence spectrums at a 350-nm excitation
53
54
55 320 wavelength (right). b) (left) Absorbance calibration curve, (middle) fluorescence
56
57 321 calibration curve at 1% of detector attenuance, and (right) fluorescence calibration
58
59 322 curve without attenuance. The fluorescence response was measured at a maximum
60
323 of 450 nm at a maximum excitation wavelength of 353 nm.

1
2
3 324 Another natural characteristic of quantum dots is their low dimensions, which range from
4
5
6
325 some nanometers to some tens of nanometers. Commonly CQDs are flake-like structures
7
8 326 with some nanometers or sub-nanometric of thickness. Those dimensions and chemical
9
10 327 compositions affect optical response, quantum yield, and color. The CQDs obtained in this
11
12
328 study were characterized by microscopy techniques, i.e., AFM and HR-TEM, to understand
13
14
15 329 their dimensions and distribution. In Figure 3, an HR-TEM micrograph and diameter
16
17 330 distribution are shown. In the micrograph, it is possible to see that the CQDs have a mean
18
19 331 diameter of 30 nm, with a range between 5 nm to 60 nm. Due to its operating principle, it is
20
21
22 332 not easy for a TEM to determine if the nanoparticles are spherical or flat or what their
23
24 333 thickness is. Hence, AFM measurements were performed.
25
26
27
28
29
30
31
32
33
34
35
36
37
38 334
39
40
41 335 Figure 3. (left) As-prepared carbon quantum dot HR-TEM micrograph and (right)
42
43 336 diameter distribution.
44
45
46 337 In Figure 4a, two AFM micrographs are shown. These micrographs were obtained by
47
48
49 338 depositing a 10 mg∙L-1 drop of CQDs on a mica surface. A high concentration of
50
51 339 nanoparticles can be observed, indicating that the individual weight of each nanoparticle is
52
53 340 very low; therefore, a large number of nanoparticles can be obtained with a low weight
54
55
56 341 concentration ratio on the order of 10 mg∙L-1. In Figure 4a, it is possible to see that the CQDs
57
58 342 have sub-nanometric thicknesses ranging from 0.5 nm to 1 nm, as measured through the
59
60 343 height profiles provided by the AFM micrographs. Furthermore, the microscopy analysis

1
2
3 344 demonstrated that the CQDs are flake-like nanostructures made up of 1 to 3 graphene-like
4
5
6
345 sheets, approximately. Ni et al.25 suggested that a single graphene sheet has the same
7
8 346 thickness as a single carbon atom, i.e., about 0.335 nm. They also proposed Raman
9
10 347 spectroscopy as an adequate technique for determining the number of graphene layers.
11
12
348 Chemical analysis was performed via UHV-XPS, and the spectra are shown in Figure
13
14
15 349 4b. The survey analysis showed that the main composition of the sample is carbon (69.2%),
16
17 350 oxygen (20.9%) and nitrogen (8.9%). Naturally, the sample contains hydrogen; however, this
18
19 351 element cannot be analyzed via XPS. High-resolution analyses, shown at the top of Figure
20
21
22 352 4b, show a wide range of organic functional groups. For oxygen, the carbonyls are present
23
24 353 as acid (≈534 eV) or isolated carbonyls (≈531.2 eV). For nitrogen, two signals were also
25
26 354 obtained, one at ≈401.2 eV that can be related to a C-N double bond, and the other at ≈398.1
27
28
29
355 eV due to the presence of amine groups. All these functional groups match well with the C1s
30
31 356 high resolution. For carbon, four well-defined main signals were obtained. The C-C and C-
32
33 357 H signal at ≈284.5 eV was used as a reference to calibrate all the spectra. This signal is the
34
35
358 smaller signal for carbon, showing that almost all the carbon atoms (92.1%) at the QD have
36
37
38 359 a bond or interaction with a heteroatom, i.e., N, O or both. This high oxygen content shows
39
40 360 that the QD have an acidic nature and high polarity, which is related to their high
41
42 361 dispersibility-affinity for water. Also, it is expected that the CQDs prepared using a natural
43
44
45 362 extract present a wide kind of organic functionalities because the extract has not only the
46
47 363 organic acid, but other different natural molecules into the solution.
48
49 364 As a complementary technique, IR was done for the as-prepared CQDS (Figure 4c). The
50
51
52
365 functional groups, as in XPS, were observed. Between 3600 cm-1 and 3200 cm-1, the signals
53
54 366 for -N-H, and -O-H, related to the amines and carboxylic acids were observed. -C-H
55
56 367 stretching was observed at a low intensity, even for sp2 (3051 cm-1) as well as sp3 (2850 cm-
57
58 1)
368 carbons. A broad signal at 1640 cm-1 related to the -C=O stretching was observed. This
59
60
369 signal has the biggest relative intensity in the spectrum, indicating that this functional group

1
2
3 370 is the main functionality of the CQDs, as was shown via XPS analysis. Aromatic carbon
4
5
6
371 overtones are also observed between 1970 cm-1 and 2200 cm-1. Qualitatively, this IR analysis
7
8 372 showed how these CQDs are aromatic carbonaceous structures with high oxygenated group
9
10 373 contents, mainly carbonyls, carboxylic acids and amines.
11
12
374 The as-prepared sample was also characterized through TGA in air. Figure 4d presents
13
14
15 375 a thermogram as percentage weight and the derivative versus the temperature. Two main
16
17 376 thermal events can be observed in the air-TGA. First, the event with a DTG maximum around
18
19 377 210 ℃ can be related to the oxidation of the residual reagents, principally from the organic
20
21
22 378 acid, which presents a maximum decomposition temperature around 200 ℃. Beyond this
23
24 379 temperature, other thermal events are present. The continuous weight loss from around 220
25
26 380 ℃ to around 500 ℃ can be related to the evolution of the organic functionalities, such as
27
28
29 381 oxygenated and nitrogenated. Hence, it is possible that the QD content of the raw material
30
31 382 after MW irradiation is about 80% by mass. In addition, this result shows that these CQDs
32
33 383 are thermally resistant, even in an atmosphere consisting of air, until 300 ℃.
34
35
36 a)
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3 b) c)
4
5
6
7
8
9
10
11
12
13
14
15
16
17 d)
18
19
20
21
22
23
24
25
26
27
28
29
384 Figure 4. a) (left)10 mg∙L-1 CQDs AFM topography micrograph (height profiles
30
31
32 385 are inside), and (right) 10 mg∙L-1 CQDs 3-D AFM side topography micrograph. b)
33
34 386 Thermogravimetric analysis (in air) of the as-prepared material after 5 min of
35
36 387 microwave irradiation (the gel-like solution, as in Figure S1). c) UHV-XPS
37
38
39 388 analysis for the as-prepared CQDs. At the top, the high-resolution spectra are
40
41 389 shown, and, at the bottom, the survey spectrum tables, including the binding
42
43 390 energies (BE in eV) and the atomic concentration in percentages, for the survey
44
45
46
391 spectrum and specified signals (O1s, N1s and C1s) are presented. d) ATR infrared
47
48 392 spectrum of the carbon quantum dots prepared in a homogeneous mixed with KBr
49
50 393 at a mass ratio of 1/100, respectively, and dried at 120 ℃ overnight.
51
52
53
54
394 A 10 mg∙L-1 CQDs dispersion in distilled water presented a pH of 3, which means, and
55
56 395 corroborates, that the CQDs have an acidic structure with a lot of carboxylic acids. Figure 5
57
58 396 shows the zeta potential and fluorescence as a function of the pH. The zeta potential has a
59
60
397 negative charge over the CQDs for a pH greater than around 3, which could indicate high

1
2
3 398 stability in the injection fluids that generally have pH values around 7, as well as subsequent
4
5
6 399 repulsion with negative charges in the porous medium surface. Below a pH value ~ 3, the
7
8 400 zeta potential becomes positive. This characteristic at high pH values shows that the CQDs
9
10 401 are acidic with a high concentration of these organic functionalities. Also, this figure shows
11
12
13
402 that as the zeta potential becomes smaller, the fluorescence decreases. These results can be
14
15 403 explained via the loss of the superficial negative charge, which allows the interaction and
16
17 404 agglomeration of the CQDs and results in a loss in quantum efficiency per gram. From pH 7
18
19
405 to a high basic pH, the fluorescence stays quasi-constant. Commonly, the tracers in the oil
20
21
22 406 and gas industry are injected in a buffered aqueous system with a roughly neutral pH. Thus,
23
24 407 these CQDs retain their original and higher fluorescence response. The stability of the CQDs
25
26 408 suspension was evaluated measuring the fluorescence over time.
27
28
29
30
31
32
33
34
35
36
37
38
39 409
40
41
42 410 Figure 5. Zeta potential and fluorescence of 10 mg∙L-1 aqueous CQDs as a
43
44 411 function of the pH. b)
45
46
47 412 In Figure 6, the stability time profiles are shown at different temperatures, including 57
48
49
50 413 °C, a representative temperature for an oil reservoir. In this figure, it is possible to see that
51
52 414 the CQDs suspensions are stable over the course of a month or even several months. In
53
54 415 addition, the temperature, 57 °C, does not affect the fluorescence response, showing that the
55
56
57
416 CQDs suspensions are stable at these evaluated conditions. It is worth to mention that the
58
59 417 sample measured after 5 months was exposed to sunlight, indicating that no significant
60

1
2
3 418 degradation of the material is observed and that it can be preserved before application in the
4
5
6
419 field without losing stability.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
420
24
25
26 421 Figure 6. CQDs stability periods for different concentrations, at room temperature
27
28 422 and at 57 °C. Evaluated via absorbance and fluorescence measurements.
29
30
31
32 423 The hydrodynamic diameter of the synthesized CQDs in distilled water and injection
33
34 424 brine was analyzed through DLS measurements at 57 °C (reservoir temperature) and
35
36 425 the results are shown in Figure 7. It can be observed that there are no major
37
38
39
426 differences between the hydrodynamic diameter distribution due to the presence of
40
41 427 the salts and is in agreement with the results reported by Kini et al.26 Slight changes
42
43 428 can be attributed to improved crosslinking between sheets and the reduction of the
44
45
429 repulsive forces, mainly driven by -stacking, hydrogen bonding and hydrophobic
46
47
48 430 interactions.27
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 431
17
18
19
432 Figure 7. Hydrodynamic diameter distribution of synthesized CQDs in distilled
20
21 433 water and injection brine at 57 °C.
22
23
24 434 3.2. Compatibility tests and oil recovery
25
26
27 435 Photographs shown in Figure 8 were taken during the compatibility test undertaken for
28
29 436 a 100 mg∙L-1 CQD dispersion and Colombian heavy crude oil in different volumetric
30
31
32
437 proportions (20/80, 50/50, 80/20). In this case, the injection brine was employed. After
33
34 438 manual shaking for 5 min and standing at reservoir temperature (57 °C) for 2 h, the system
35
36 439 is inspected visually in order to determine if it contains emulsions or agglomerations in the
37
38
440 aqueous or oil phases. This result guarantee that no additional phases are formed and discards
39
40
41 441 any source of formation damage due to fluid-fluid incompatibility.28 In Figure 8, it can be
42
43 442 seen that the presence of 100 mg∙L-1 of CQDs do not affect the interaction between water and
44
45 443 the heavy crude oil. No emulsion or aggregation was observed for any CQDs
46
47
48 444 dispersion/crude oil ratio. In addition, under UV irradiation, it was shown that the CQDs in
49
50 445 all three ratios presented the same optical responses before and after the compatibility test.
51
52 446 Hence, the partition coefficient O/W for the CQDs is practically null. At the right side of the
53
54
55
447 Figure 8, the photonic responses, i.e., the fluorescence, of the CQDs after the different
56
57 448 compatibility tests and in different matrices can be observed. As the photographs show, the
58
59 449 fluorescence does not change significantly during the interaction with the crude oil,
60
450 confirming that the O/W partition coefficient of the CQDs is practically null. In additional,

1
2
3 451 it is also possible to see that the photonic response of the CQDs related to their fluorescence
4
5
6
452 does not decrease significantly in the presence of the injection reservoir brine, even in
7
8 453 presence of silica nanoparticles at high concentration.
9
10
11
12
13
14
15
16
17
18
19 454
20
21 455 Figure 8. Left: Photographs taken during the compatibility test (100 mg∙L-1 CQDs
22
23
24
456 with crude oil). Right: Fluorescence for a 100 mg∙L-1 CQDs dispersion after the
25
26 457 different compatibility tests.
27
28
29 458 One of the important parameters in an injecting or stimulating fluid for oil recovery is
30
31 459 its rheological performance, including viscosity and interfacial tension. Figure 9 shows the
32
33
34 460 viscosity for different concentrations of CQDs in distilled water and injection brine, as well
35
36 461 as the interfacial tension W/O for different concentrations of CQDs and in different matrices.
37
38 462 The analysis showed that the viscosity increased somewhat when the concentration of the
39
40
41 463 CQDs increased an order of magnitude, for example, a 40 % increase in viscosity for an
42
43 464 incremental increase from 1 mg∙L-1 to 1000 mg∙L-1. Nevertheless, the increase in viscosity is
44
45 465 not enough to improve the sweep efficiency in the reservoir as in the case of other related
46
47
48
466 nanofluids.29 On the right side of Figure 9, it is possible to see the interfacial tension between
49
50 467 different systems. Distilled water/toluene does not show a significantly variance when the
51
52 468 CQDs are added at various concentrations (0 mg∙L-1 to 1000 mg∙L-1). Typically, injection
53
54 469 water decreases the W/O IFT due to the ionic force and natural ions present in the reservoir.
55
56
57 470 In the figure, it can be seen that the IFT injection of water/crude oil is almost half that for the
58
59 471 reference system (distilled water/toluene). As in the case of the viscosity, the IFT using the
60
472 injection water, which contain real ions and has an ionic force, and toluene or crude oil

1
2
3 473 increases as the concentration of CQDs increases. However, the increasing is not significant,
4
5
6
474 changing from 14 mN∙m-1 at 1 mg∙L-1 to 18 mN∙m-1 at 1000 mg∙L-1. Thus, there was not even
7
8 475 a 20% increase in IFT with an increase of three magnitude orders in the concentration of the
9
10 476 CQDs. This result shows, as did Figure 8, that the presence of CQDs in the injection water
11
12
477 does not promote emulsion or agglomeration, even at high concentration such as 1000 mg∙L-1.
13
14
15 478 Compatibility tests were performed for a wide range of concentrations of CQDs. Commonly,
16
17 479 commercial inter-well tracers are injected at concentrations between 1 mg∙L-1 to 100 mg∙L-1.
18
19 480 Therefore, the compatibility tests showed that the CQDs can be used as a tracer without
20
21
22 481 significant changes in the physical-chemical performance of the injected fluid.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38 482
39
40 483 Figure 9. Viscosity of the water at different concentrations of CQDs (left).
41
42
43 484 Interfacial tensions between different concentrations of CQDs in water and toluene
44
45 485 (right).
46
47
48 486 Figure 10 shows how the CQDs are retained at the porous media, as evaluated with a
49
50
51
487 micro-lab-scale sand pack. In this figure, it is possible to see that the CQDs has a
52
53 488 breakthrough around 1 pore volume injected, indicating that they have no significant
54
55 489 interaction with the porous media. This is due to the repulsion forces between the surface of
56
57
490 the silica sand that have mainly negative charges and the acidic functional groups of the
58
59
60 491 material, which are also negatively charged at the experimental condition (pH ~ 7). Our

1
2
3 492 results were compared with the injection of KI as a tracer commonly employed in the oil and
4
5
6
493 gas industry, where it can be seen that the retention profile is similar than for the CQDs and
7
8 494 is in concordance with those reported by Agenet et al. 30
9
10 a)
11
12
13
14
15
16
17 b)
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
495 Figure 10. a) Retention profile, and b) cumulative CQD production in a
36
37
38 496 micromodel using synthetic sea sand and a 100 mg∙L-1 concentration of CQDs.
39
40 497 Profiles are compared with the retention of KI to secure similar results in
41
42 498 traceability processes.
43
44
45
46 499 Figure 11 shows a) retention profile, b) cumulative CQD production, and c) oil recovery
47
48 500 results for the displacement tests performed in a core sample. Here, the experiments were
49
50 501 also made for KI for comparison issues. The breakthrough is observed around 0.8 porous
51
52
53
502 volumes (PV), which is coherent data for the displacement when taking into account that
54
55 503 when injected under high pressure and temperature, some preferential channels are generated
56
57 504 by which the tracer arrives first at the break. Similarly, there is a retention of the tracer in the
58
59
505 middle after the injection of brine. In this study, a sweep of CQDs after 0.8 porous volumes
60
506 and the injection brine was observed, and a sweep of about 99% of the CQDs was obtained

1
2
3 507 after 3 PV are injected with the brine as it can be seen in Figure 11b. The obtained curve
4
5
6
508 resembles the curves done for KI tracer by Agenet et al.,30 showing that the chemical nature
7
8 509 of the CQDs produces the typical qualities of a tracer without affecting the physicochemical
9
10 510 properties of a field.
11
12
511 It is possible to see from Figure 11c that a 1000 mg∙L-1 CQDs dispersion in a brine can
13
14
15 512 recover around 65% of the crude oil. When switching to a minor CQDs dispersion, no more
16
17 513 crude oil can be recovered. Hence, the oil recovery is the same with or without CQDs added
18
19 514 to the injection fluid. For this case, only the reservoir brine is injected as a flood fluid. These
20
21
22 515 results are in accordance with the compatibility tests for which the presence of the CQDs, at
23
24 516 different concentrations, does not affect significantly the physical-chemical properties of the
25
26 517 different fluids and has no affinity for the oil phase.
27
28
29
a) c)
30
31
32
33
34 b)
35
36
37
38
39
40
41
42
43
44 518 Figure 11. Displacement results for CQDs in a Colombian field core at field
45
46
47 519 pressure and temperature conditions: a) retention profile, b) cumulative CQD
48
49 520 production, and c) oil recovery results. A 100 mg∙L-1 CQDs dispersion in injection
50
51 521 brine was used. Profiles are compared with the retention of KI to secure similar
52
53
54 522 results in traceability processes.
55
56
57 523
58
59
60 524

1
2
3 525 3.3. Field trial results
4
5
6 526 Figure 12 shows the rupture curves of some wells evaluated in the field. In the right
7
8 527 figure, the tracer bursts 3 days after injection, at a concentration of 3.1 mg∙L-1, continues
9
10
11 528 increasing for 15 days to a maximum concentration of 41.3 mg∙L-1and later declines to 2.5
12
13 529 mg∙L-1 25 days later. In the left figure, the tracer bursts 3 days later at a concentration of 4.2
14
15 530 mg∙L-1, continues to increase for 3 days to a maximum value of 15.4 mg∙L-1 and declines to
16
17
18
531 1.4 mg∙L-1 8 days later. It is worth to mention that the available injection/production data of
19
20 532 the wells prior CQDs injection allowed the verification of inter-well traceability and
21
22 533 corroborated the good performances of this nanomaterial as green tracers. Also, the
23
24
534 operation-related costs decreased more than 70% in comparison to previous tracers employed
25
26
27 535 in the field, and are mainly related to the CQDs costs production of around 50 USD/kg,
28
29 536 effluent sampling, and time of analysis.
30
31
32
33
34
35
36
37
38
39
40
41
42 537
43
44
45 538 Figure 12. CQDs tracer test in a Colombian field during a conventional
46
47 539 waterflooding operation. The concentration of the CQDs at the producer wells is a
48
49 540 function of time. The CQDs were injected as a concentrated (500 000 mg∙L-1)
50
51
52 541 batch.
53
54
55 542 The advance of the development of this technology is, at present, around TRL 8. Some
56
57 543 companies are involved in the industrial production of the tracers and the field applications.
58
59
60
544 These results in the field and forthcoming research and development work will open a broader
545 landscape for nanomaterials and nanotechnology based on exotic fruits and agricultural

1
2
3 546 residues to be used in developing new technologies for the oil and gas industry in Colombia.
4
5
6
547 In addition, the possibility exists for the development of advanced instrumentation for the
7
8 548 identification and quantification of CQDs in-line and in-real-time, such as portable
9
10 549 fluorimeters with wireless connections.
11
12
550
13
14
15
16 551 4. Conclusions
17
18
19
552 In this work, it was shown that the CQDs can be prepared easily and cheaply. A wide
20
21 553 range of organic compounds can be used for their preparation, including natural extracts, as
22
23 554 was the case in this study. Microwave assisted carbonization (MWC) is an economical and
24
25
555 quick procedure that can be used to obtain these kinds of nanomaterials (CQDs), especially
26
27
28 556 when compared to electrochemical and hydrothermal procedures. In addition, the equipment
29
30 557 is easy to buy or find in a normal laboratory (domestic microwave oven and conventional
31
32 558 glassware). Using the MWC process, it is possible to obtain large quantities of CQDs with
33
34
35 559 concentrations higher than a mass fraction of 80% in only 5 minutes. The instrumental
36
37 560 characterization revealed that the obtained carbogenic materials were quantum dots with
38
39 561 nanometric diameters and sub-nanometric thicknesses that had high nitrogen and oxygen
40
41
42
562 contents, thus favoring interactions with the aqueous phase. All the compatibility tests
43
44 563 showed that the obtained CQDs do not change the physical-chemical properties of the
45
46 564 injection fluids and their interactions with crude oil significantly. During the displacement
47
48
565 with and without crude oil, using a lab-micro-system of Ottawa sand pack and real cores from
49
50
51 566 a Colombian field, it was observed that the CQDs are minimally retained in the porous media,
52
53 567 have a breakthrough of around 1 pore volume injected and reach the original inlet
54
55 568 concentration. In addition, the CQDs can be removed completely once they are eliminated
56
57
58 569 from the injected fluid. In conclusion, the CQDs can be used as an economical, easy-to-track-
59
60 570 and-analyze, non-toxic, non-polluting tracer for the Colombian oil industry. The field trial

1
2
3 571 test showed that CQDS are useful and superior to traditional flourobenzoic derivates as green
4
5
6
572 inter-well tracers for the oil and gas industry.
7
8 573
9
10
11 574 Acknowledgments
12
13
575 The authors acknowledge ECOPETROL and Universidad Nacional for the funding received
14
15
16 576 for this study and logistical support.
17
18
19 577 References
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