Sustainable Biocement Production via Microbially Induced Calcium

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Sustainable biocement production via microbially-induced calcium carbonate precipitation: use of limestone and acetic acid derived from pyrolysis of lignocellulosic biomass Sun-Gyu Choi, Jian Chu, Robert C. Brown, Kejin Wang, and Zhiyou Wen ACS Sustainable Chem. Eng., Just Accepted Manuscript • Publication Date (Web): 16 May 2017 Downloaded from http://pubs.acs.org on May 17, 2017

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ACS Sustainable Chemistry & Engineering

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Sustainable biocement production via microbially-induced calcium

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carbonate precipitation: use of limestone and acetic acid derived from

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pyrolysis of lignocellulosic biomass

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Sun Gyu Choi,† Jian Chu,† Robert C. Brown,‡ Kejin Wang,s and Zhiyou Wen*,§

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†

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50 Nanyang Ave, Singapore 639798.

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‡

Bioeconomy Institute, Iowa State University, 617 Bissell Road, Ames 50011, IA, USA.

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s

Civil, Construction and Environmental Engineering, Iowa State University, 813 Bissell Road,

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Ames 50011, IA, USA.

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§

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IA, USA.

School of Civil and Environmental Engineering, Nanyang Technological University, 10 Blk N1,

Food Science and Human Nutrition, Iowa State University, 536 Farm House Lane, Ames 50011,

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* Corresponding author: Zhiyou Wen ([email protected])

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Synopsis: The use of limestone from aggregate quarries and acetic acid from pyrolysis of

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lignocellulosic biomass is an effective and environmental friendly method to produce biocement.

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ABSTRACT: Biocement production from microbially-induced calcium carbonate precipitation

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(MICP) is an environmental friendly approach for construction works, but the use of calcium

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chloride (CaCl2) in the conventional MICP process is a cost-limiting factor. The aim of this work

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is to develop a method for producing soluble calcium ions through two waste sources, limestone

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powder derived from aggregate quarries and acetic acid derived from fast pyrolysis of

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lignocellulosic biomass, as a replacement of the reagent grade CaCl2 in the MICP process. The

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ratio of limestone powder to acetic acid solution was optimized for a desirable calcium

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concentration with an appropriate pH. Procedures for applying the urease-producing bacteria,

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urea and calcium solutions were developed for a successful MICP process, and were treated for

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sand column test. Engineering properties of the biocemented sand, including water permeability,

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unconfined compressive strength, and tensile strength, were evaluated as a function of the

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calcium carbonate content of the product. It was found that the properties of the sand treated

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using the limestone/acetic acid derived calcium solution were comparable to those treated using

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reagent grade CaCl2. Collectively, the results indicate that the new MICP process is effective,

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more sustainable and cheaper compared with the conventional MICP method.

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KEYWORDS: Biocementation, permeability, strength, limestone, acetic acid

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■ INTRODUCTION Cement-based materials (grout, mortar, and concrete) have been widely used for

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construction and infrastructures repair.1 The production of cement is energy-intensive and

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environmentally unfriendly due to the requirement for burning limestone at a very high

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temperature (950oC) and the emission of carbon dioxide. It is reported that production of one ton

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of Portland cement generates approximately 0.814 ton of carbon dioxide (CO2) from calcining

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limestone and fuel use. 2 Cement production contributes about 5% of global CO2 emissions.

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In the recent years, an environmentally friendly bio-based cement material has been

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developed for geotechnical applications.3-5 Biocement is a construction material that can be made

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from calcium salt (Ca2+), a small amount of urea (CO(NH2)2), and urease-producing bacteria

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(UPB). The mechanism for using biocement as construction materials is called microbially-

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induced calcite precipitation (MICP), which is described by the reactions:

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UPB

2 NH4+ + CO32-

CO(NH2)2 + 2H2O Ca2+ + CO32-

CaCO3 ↓

(1) (2)

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where carbonate (CO32-) is produced from urea decomposition that is catalyzed by UPB.

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Carbonate then reacts with calcium ions to form calcium carbonate (CaCO3) in situ, which can

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fill small pores, bridge cracks, and bind loose particles.6-7

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Biocement can be used for both construction and concrete repair.8,9 It can be used in a

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manner similar to that for cement to reduce the hydraulic conductivity and increase the shear

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strength of soil as well as repair cracks in concrete. Cement grout is made of cement, water, and

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sometimes fine aggregate. Biocement can be used to make grout in more or less the same way as

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for cement grout, but can increase the shear strength or decrease the hydraulic conductivity of

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soil.10 Various studies have been conducted on the use of biocement grouting to replace 3 ACS Paragon Plus Environment


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conventional cement grouting. These include dust control,11 construction of landfill for solid

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waste disposal, stabilization of slopes or levees,12 mitigation of liquefaction of soil,13 seepage

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control for underground construction, and construction of aquatic pond in sand.14

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Compared to Portland cement, the use of biocement has several advantages. First, the

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production of biocement consumes much less energy. Biocement is produced at an ambient

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temperature 20 oC-40oC, while the temperature for cement production is 950oC. Second, the

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viscosity of biocement-based grout is much lower than that of Portland cement-based grout, thus

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biocement can be more easily injected into the ground or mixed with soil than Portland cement.

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Third, the particle sizes of biocement are smaller than those of Portland cement; therefore,

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biogrout can be permeated into porous materials (e.g., soil and concrete) and seal finer fissures in

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pores and cracks than Portland cement grout. Because of these advantages, biocement has

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potential to play a significant role in the next generation of sustainable construction materials.

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Nevertheless, it should be noted that the applications of biocement are mainly limited to

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geotechnical problems as described above. It is not intended as a complete replacement of

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Portland cement.

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However, the use of MICP-based biocementation has also challenges. The MICP process

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usually requires a large amount of calcium chloride (CaCl2) as a calcium source,15-17 which is

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expensive and environmentally unfriendly.18 Efforts have been made to develop alternative

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calcium sources. For example, Plant-induced calcite precipitation (PICP) process that used

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urease reactive jack bean and calcium hydroxide and/or calcium nitrate for sand cementation.19

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another research used calcium nitrate and acetate as a calcium source to replace CaCl220 calcium

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source using eggshell and vinegar.21 Those methods, however, are either unsuitable for large

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scale application or not economically competitive. 4 ACS Paragon Plus Environment

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To address the above limitations, this study reports a new and cost effective method for

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producing calcium ions using waste materials and its application in biocementation. A limestone

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powder derived from aggregate quarries and an acetic acid derived from fast pyrolysis of

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lignocellulosic biomass were used as raw materials for producing calcium ions. Limestone is a

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large quantity of waste materials in aggregate. Similarly, acetic acid is a major byproduct in fast

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pyrolysis of lignocellulosic biomass. Fast pyrolysis of lignocellulosic biomass is the

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decomposition of the organic matters in the biomass without oxygen. The process has proved as

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a promising approach to produce drop-in fuels from lignocellulosic biomass. The pyrolysis

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process, however, commonly produce a significant amount of acetic acid as a byproduct.22 The

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disposal of this acetic acid stream is challenging for cellulosic biofuel industry.23 In this work,

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we use this acetic acid stream to dissolve calcium from the limestone powder. The produced

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calcium ions were used for biocement production through MICP process. The aim of the current

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study is to explore the feasibility of this unique approach and to optimize the reaction conditions

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of acetic acid and limestone for a maximum calcium solution production. A MICP process using

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the produced calcium ion was applied for sand cementation. The engineering properties of the

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biocemented sand was evaluated.

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■ EXPERIMENTALS

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Urease Producing Bacteria (UPB) culture. Sporosarcina pasteurii (ATCC 11859) was

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used as the urease producing bacterium (UPB).5,24 The bacterial cells were grown in medium

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containing (per liter) 20 g yeast extract, 10 g ammonium sulfate, and 0.13 M Tris buffer

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(pH=9.0).25 The medium was autoclaved at 121°C for 15 minutes. The culture was maintained in

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a shaker (130 rpm) at 30°C for 2 days. 5 ACS Paragon Plus Environment


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Cell growth was monitored by measuring optical density (OD) of the broth at 600 nm. When

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ready to be used, the UPB solution had a OD600 range 1.0-1.6, similar to previous reports.26,27

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The urease activity of the UPB solution was measured using an electric conduct-meter.28 It

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measured with a range from 8 to 15 mM/min, also similar to those reported previously.26,29

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Preparation of calcium ion solution. Calcium ion solution was produced by dissolving a

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limestone powder in an acetic acid-rich solution. The limestone powder was obtained from the

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Martin Marietta limestone quarry in Ames, Iowa, USA. It had a particle size passing # 200

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screen (less than 0.075 mm) and a specific gravity of 2.70. The limestone contained 50.7% (by

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weight) CaO as a major composition, with small amount of SiO2 (2.39%), Al2O3 (0.85%) and

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Fe2O3 (0.35%).

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The acetic acid rich stream was received from the Bioeconomy Institute at Iowa State

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University in Ames, Iowa, USA. The stream was a byproduct from the fast pyrolysis of

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lignocellulosic biomass for producing drop-in fuels.30 It contained more than 7% (w/v) acetic

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acid with relatively small amount of acetol (5.06%), total phenolics (2.09%) and formic acid

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(1.22%). The calcium ion is produced as follows,

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CaCO3 + 2CH3COOH

Ca2+ + 2(CH3COO)- + CO2 + H2O

(3)

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To optimize the ratio of limestone to acetic acid, limestone powder (100 g) was mixed with

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acetic acid solution (200, 400, 800, and 1200 ml) at different ratios (w/v), i.e. 1:2, 1:4, 1:8, and

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1:12, respectively. After 5-day reaction at room temperature (~25oC), calcium concentration and

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pH values of limestone/acetic acid mixture solution were determined. As shown in Table 1, the

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resulted solution contained calcium ion ranging from 0.83-0.64 M and pH from 5.2-4.8.


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Our previous research has demonstrated that the raw acetic acid stream derived from biomass

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pyrolysis contains various compounds such as acetol, 5-hydroxymethylfurfural (HMF),

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phenolics and furfural, which are strong inhibitors for bacterial growth.22,23 Considering the case

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that 800 ml acetic acid solution resulted in a relatively high calcium concentration with a large

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volume, and the fact that 1,200 ml acetic acid contains substantial inhibitory compounds, the 800

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ml acetic acid solution was selected for producing calcium ions in the following MICP process

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development.

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The calcium solution prepared from 800 ml acetic acid solution was further added with

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distilled water to adjust the final calcium ion concentration to 0.3 M. The pH of this solution was

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further adjusted to 7.0-7.5 using ~4.5 g sodium hydroxide pellets. The solution was then

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centrifuged at 4,000 rpm for 20 minutes to obtain supernatant, which serves as the final calcium

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ion solution in the following MICP processes in both free solution and sand column tests.

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Development of MICP-based biocementation process in free solution tests. The MICP

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process for biocementation was illustrated in Scheme 1. The UPB culture broth (30 ml) grown

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for 2 days with a density of OD600=0.8-1.2 was mixed with 0.3 M urea solution (30 ml) at a ratio

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of 1:1 (v/v). The mixture had a pH 7.0 to 7.5 and was stored in a beaker for one day, and then

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added with calcium solution (30 ml) which was prepared based on the procedures described in

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previous section (Preparation of calcium ion solution). Precipitation was observed immediately

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after addition of the calcium solution. This precipitated material was filtered out by FG/C filter

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paper and dried at 115°C for 1 day. The dried material was then analyzed using x-ray diffraction

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(XRD).

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Development of MICP-based biocementation in sand column tests. A total six sand

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columns were tested for MICP-based biocementation. The schematic setup of the MICP-based

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sand column biocementation test is shown in Scheme 2. As shown in the scheme, sands (U.S.

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Silica Company‘s Ottawa plant in Ottawa, IL) were placed in a PVC cylinder (5-cm diameter

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and 10-cm length) in 10 layers with a density of approximately 1.70 g/cm3. Two pieces of 3M

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Scotch-Brite scouring pads were placed at each end of the sand column as filters. The PVC

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cylinder was placed on a funnel filled with gravel. A beaker was used to collect the solution

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penetrating through the sand column, which was then circulated to the top of the column.

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To implement MICP-process, 80 ml UPB seed solution was placed in the beaker and

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recirculated through a peristaltic pump to the top of the sand column (Scheme 2). The pumping

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rate was controlled at 1.5 to 2.0 ml/min. The liquid circulation was run for 3 hours to ensure the

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UPB cells evenly distributed within the column. Then, the solution in the beaker was replaced

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with a mix of fresh UPB seed solution (30 ml), urea solution (150 ml at 0.3M) and calcium

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solution (150 ml at 0.3 M). The calcium solution was prepared based on the procedures

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described in previous section (Preparation of calcium ion solution). This mixed solution was

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recirculated through the column for 9 hours. The above recirculation procedure (3 hours of UPB

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seed and 9 hours of UPB/urea/calcium solution) was repeated twice a day for 7 days, at which

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calcium carbonate began to precipitate in the column.31 The recirculation procedure was

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continued for another 3 days. After being treated for a total of 10 days, the outlet from the

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column was blocked completely. The cemented sand column was then washed with distilled

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water, and the outer cylinder layer was removed.

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Evaluation of the properties of the biocemented sand columns. The cemented sand columns were tested to evaluate its engineering properties including water permeability, 8 ACS Paragon Plus Environment

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unconfined compressive stress (UCS), tensile stress (TS), microstructure image, and the CaCO3

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content. To carry out the permeability, the sand column (both before and after MICP treatment)

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was soaked in distilled water for 24 hours and then subject to a constant head based on the

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ASTM D 2434 method.32 The sand columns were then placed at 23°C and 50% RH conditions

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for a two-day prior to the UCS and TS tests based on the ASTM D 4219 and ASTM C 496

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methods, respectively.33,34 Among six sand columns tested, three were used for UCS tests

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(designated as UCS1, UCS2 and UCS3) and the other three for TS tests (designated as TS1, TS2,

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and TS3). About 5 grams of biocemented sand samples were collected from the centers of the

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failed sand columns for the microstructure image observation through a scanning electron

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microscope (SEM) and for the determination of the CaCO3 content using the ASTM D4373

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method.35

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■ RESULTS Confirmation of the MICP process from limestone and acidic acid in free solution tests.

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The precipitated material produced from the MICP process using acetic acid and limestone.

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These precipitated materials were analyzed by XRD (Figure 1). The XRD pattern of the

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precipitated materials (Figure 1a) was perfectly matching with that of the pure reagent grade of

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calcium carbonate (CaCO3) (Figure 1b). The result confirms that the precipitate was indeed

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CaCO3, and validated the use of acetic acid derived from biomass fast pyrolysis and the

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limestone to produce calcium carbonate in the MICP process. In the following work, sand

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column tests were conducted to evaluate the effectives of the this unique MICP-process.

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CaCO3 content and permeability of the sand columns. The CaCO3 content of the

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cemented sand ranged from 5.67% to 8.19%. This was within the CaCO3 content range used in

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previous studies where reagent grade CaCl2 was used in the MICP process.31 The variation in the

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CaCO3 contents in the six sand columns was due to the experimental variations such as the liquid

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flow patterns inside the sand columns, the surface areas of the sands in each column, etc.

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The water permeability of the cemented sand is plotted as a function of the CaCO3 content in

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Figure 2, along with the permeability of the un-treated sand as a comparison. It can be seen that

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the permeability has reduced from 1×10-4 m/s for un-treated sand to 8.17-1.52×10-6 m/s for

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MICP treated sand. This is similar to the observation made in previous studies 31 that the

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permeability of the MICP treated sand decreases with the CaCO3 content nonlinearly.

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Strength of the sand columns. Figure 3 shows unconfined compressive stress (UCS) and

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tensile stress (TS) as functions of the axial strain of the cemented sand columns. As shown in the

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figure, the stress-strain behaviors were similar for each set of UCS or TS tests.

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Based on the data in Figure 3, the strength values obtained from the UCS and TS tests are

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plotted as a function of CaCO3 contents, respectively. As shown in Figure 4a, both UCS and TS

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strengths of the cemented sand increased with calcium carbonate content, which is similar to the

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previous studies.6,21 The trend lines of the UCS and TS vs CaCO3 contents were also determined

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with a high correlation coefficients (R2) obtained within the calcium carbonate content range of

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5.5 to 8.5 %. (Figure 4a).

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The UCS/TS strength ratio of the treated sand is also presented to monitor its brittleness

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(Figure 4b). In general, the higher the UCS/TS strength ratio the more brittle the material. The

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strength ratio can change with rock types from 2.7 to 39 with an average of 14.7.36 Here the 10 ACS Paragon Plus Environment

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strength ratio was determined based on the two regression curves in Figure 4a. A series of

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hypothetical CaCO3 contents (5%-9%) were selected to cover the true CaCO3 contents in this

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work. Under each hypothetical CaCO3 content, the UCS and TS strength values were determined

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based on their corresponding regression equations in Figure 4a. The UCS/TS strength ratio was

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then calculated and plotted as a function of the corresponding CaCO3 contents (Figure 4b). As

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shown in Figure 4b, the strength ratio increased with calcium carbonate content. At 9% of

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CaCO3, the column has a strength ratio of 6.87. It should be noted that the UCS/TS strength ratio

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can be extrapolated as 7.3-7.6 at a calcium carbonate content of 11 to 13%, which are almost

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same strength ratio as reported at the same calcium carbonate content but using calcium chloride

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for the MICP process.31 The results in Figure 4b also suggests that when the calcium carbonate

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content of the MICP-treated sand is within 5-9%, the brittleness of the MICP-treated sand is less

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than the rock materials.

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Microstructure of MICP treated sand columns. The microstructure of the biocemented

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sand column are shown in Figure 5. Figure 5a shows that after the MICP treatment, sand particle

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surfaces were covered with CaCO3. Clumps of CaCO3 also filled the spaces between the sand

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particles (area “A”). Figure 5b illustrates the particles bridged by CaCO3. Figure 5c indicates that

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CaCO3 covered the sand surface with a size approximately ranging from 5 to 20 µm, which is

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comparable to those observed from the previous MICP study where reagent grade CaCl2 was

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used as the calcium source.31

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In some other areas of the sand column, precipitated CaCO3 with different morphology was

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observed. For example, loosely packed, smaller size sphere-shaped CaCO3 crystals with radial

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striations were observed Figures 5d-5f. The difference morphology of CaCO3 crystals might be



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related to bacteria types, calcium sources, and medium types.20 Further study is needed to study

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the factors affecting the formation of CaCO3 morphology in different MICP processes.

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■ DISCUSSION Portland cement is the most common material used for soil improvement. However, use of

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Portland cement has severe environmental issues such as greenhouse gas emission and high

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energy consumption. The development of quarries for cement materials also damages the natural

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forest and inhabitants. Biocement produced through the MICP process is a new and eco-friendly

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cementation material that can reduce the problems related to the use of Portland cement.37

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Currently, the commercialization of biocement production is facing several challenges such

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as the high material cost. For example, calcium chloride is commonly used as a source of

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calcium ion in the MICP process at a price about $20-60/m3.38 This study confirmed that the

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acetic acid derived from biomass fast pyrolysis, together with the limestone waste from

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aggregate quarries, are capable of producing soluble calcium ions. The XRD curve of the

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precipitated materials in the free solution test confirmed the successful implementation of the

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MICP-process based on these two waste materials. It should be noted that this lab-scale

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feasibility study did not provide a thorough analysis of production cost. With the optimization of

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various operation procedures, the cost of biocement production proposed in this work can be

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competitive to the conventional CaCl2-based biocement. For example, centrifugation was used to

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prepare a clean calcium ion solution in this lab-scale study. In the large-scale operation, the

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centrifugation operation can be replaced by cost effective solid-liquid separation methods such as

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filtration or sedimentation. The particle size of limestone powder can also be optimized to

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produce a best calcium ion dissolving efficiency. 12 ACS Paragon Plus Environment

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The biocement production reported in this work also represents a more sustainable approach

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producing biocement. For example, chloride ions (Cl-) derived in the CaCl-based biocement

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production can negative affect freshwater microorganisms and in natural plants and also induce

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the corrosion of the steels reinforcement of the construction works.39 Producing calcium ions by

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limestone derived from aggregate quarries and acetic acid derived from lignocellulosic biomass

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fast pyrolysis is a cost effective and environmental friendly method for providing this important

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materials for MICP process. Unlike chloride, acetate ion has a less negative impact to the

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environment and can be readily degraded by natural microorganisms. Another suitability

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characteristics of this work is the use of acetic acid byproduct derived from biomass fast

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pyrolysis. Fast pyrolysis of lignocellulosic biomass has been widely studied as an effective

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approach for producing bio-oil that can be upgraded into drop-in fuels.40 During biomass

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pyrolysis process, however, acetic acid is produced as one major chemical constituent of

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pyrolysis-derived bio-oil, and is often viewed as a corrosive contaminant rather than a valuable

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product. The coupling of using this waste acetic acid with the biocement production can not only

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produce an environmental friendly construction material, but more importantly, provide an outlet

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for using acetic acid rich byproducts of biomass fast pyrolysis process.

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In general, factors such as urease activity,26 concentrations of chemicals used,27 degrees of

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saturation41 and types of calcium19,20 were all influencing the engineering properties of the

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cemented sand columns. The engineering properties of the sand column obtained from the acetic

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acid and limestone waste materials was compared to those of the sand columns using the reagent

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grade CaCl2. For example, Figure 6 demonstrates the UCS of sand columns cemented from

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different MICP processes. As shown in Figure 6, the UCS values increased with increasing

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calcium carbonate content for all the cases. Feng and Montoya reported that engineering 13 ACS Paragon Plus Environment


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properties (cohesion, friction angel and shear strength) of cemented sands increased compare to

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the untreated sand due to the bonding of the sand particles by calcium carbonate precipitation,

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and high calcium carbonate content led to a stronger bonding.42 The UCS vs calcium carbonate

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trend line obtained in this work was in the similar range as those for other sand columns and was

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in particular similar to the column reported by Qabany and Soga (Figure 6).27 From these

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comparison, it can be concluded that the sand column cemented from waste limestone powder

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acetic acid can be an effective approach for MICP-based biocementation.

307

This work has demonstrated a novel approach to produce biocement materials using

308

limestone waste and acetic acid byproducts derived from lignocellulosic biomass pyrolysis.

309

However, it should be noted that MICP-based biocementation has also other challenges such as

310

emission of ammonia due to high pH, and difficulty to apply fine soil (silt or clay) due to the

311

small particle size of bacteria and precipitated calcium carbonate.3 More researches are needed to

312

solve those problems so the MICP biocementation can be applied in various soil types and real

313

ground and this is under way.43

314 315 316

■ CONCLUSIONS This paper reported the development and evaluation of a new MICP process by using waste

317

limestone from an aggregate quarry and acetic acid from the fast pyrolysis of lignocellulosic

318

biomass. A new soluble calcium source has been obtained from a mixture of limestone powder

319

and acetic acid with pH adjustment. Such a calcium solution can replace CaCl2 for production of

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precipitated CaCO3 via MICP. The sand columns treated using the new calcium sources

321

demonstrated similar engineering properties as those of treated using CaCl2.

322 14 ACS Paragon Plus Environment

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■ AUTHOR INFORMATION

324

Corresponding Author

325

*E-mail: [email protected]

326

Notes

327

The authors declare no competing financial interest.

328 329

■ ACKNOWLEDGMENTS

330

The authors would like to thank the Midwest Transportation Center, the U.S. Department of

331

Transportation Office of the Assistant Secretary for Research and Technology for sponsoring this

332

research. All experiments were performed at Iowa State University. Special thanks are given to

333

Dr. Xuefei Zhao, Ms. Yu Tian and Ms. Huahua Ouyang, all from Iowa State University, for their

334

assistances in some of the present experimental work.

335 336

■ REERENCES

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443 444


Table 1. Different ratios of limestone powder to acetic acid solution used for preparing calcium ion solution. Limestone powder (g) 100

Acetic acid Solution (ml) 200

Calcium ion concentration (M) 0.83

pH 5.2

100

400

0.80

5.1

100

800

0.76

5.0

100

1,200

0.64

4.8

445 446



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List of Schemes:

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Scheme 1. Schematic illustration of the MICP process in free-solution tests.

449

Scheme 2. Experimental setup for MICP-based biocementation in sand column tests.

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452 453

Scheme 1. Schematic illustration of the MICP process in free-solution tests.

454 455



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456

457 458 459 460 461

Scheme 2. Experimental setup for MICP-based biocementation in sand column tests


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List of Figures:

463

Figure 1. XRD results of the materials precipitated from the MICP process (A), and pure reagent

464

grade calcium carbonate (B). The MICP process was performed in free solution with

465

limestone powder and acetic acid solution derived from lignocellulosic biomass.

466 467 468

Figure 2. Permeability of MICP-treated sand as a function of CaCO3 content in the sand column. Permeability of untreated sands is also presented as a baseline. Figure 3. Strain-stress relationship of the sand columns cemented with MICP process using

469

limestone powder and acetic acid solution derived from lignocellulosic biomass. (A)

470

Unconfined Compression (UC), and (B) Splitting Tensile (TS).

471

Figure 4. Strength (maximum unconfined compressive stress (UCS) and tensile stress (TS)) of

472

the sand columns as functions of the CaCO3 content in the columns (A); and strength

473

ratio of UCS to TS (B).

474

Figure 5. SEM Images of MICP-based cemented sand columns. The MICP process was prepare

475

in free solution with limestone powder and acetic acid solution derived from

476

lignocellulosic biomass.

477

Figure 6. Comparison of UCS obtained from this study with the UCS reported from other

478

studies. All the columns were cemented using the similar chemical concentration (0.2 to

479

0.5 M of urea and calcium solution.

480



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481

482 483 484 485 486 487

Figure 1. XRD results of the materials precipitated from the MICP process (A), and pure reagent grade calcium carbonate (B). The MICP process was performed in free solution with limestone powder and acetic acid solution derived from lignocellulosic biomass.


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Water permeability (m/s)

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488 489 490 491

Figure 2. Permeability of MICP-treated sand as a function of CaCO3 content in the sand column. Permeability of untreated sands is also presented as a baseline.

492 493



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494

495 496 497 498 499

Figure 3. Strain-stress relationship of the sand columns cemented with MICP process using limestone powder and acetic acid solution derived from lignocellulosic biomass. (A) Unconfined Compression (UC), and (B) Splitting Tensile (TS).

500 501


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502 503

Strength rato (UCS / TS)

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504 505 506 507 508

Figure 4. Strength (maximum unconfined compressive stress (UCS) and tensile stress (TS)) of the sand columns as functions of the CaCO3 content in the columns (a) and strength ratio of UCS to TS (b).



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Figure 5. SEM Images of MICP-based cemented sand columns. The MICP process was prepare in free solution with limestone powder and acetic acid solution derived from lignocellulosic biomass.


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Figure 6. Comparison of UCS obtained from this study with the UCS reported from other studies. All the columns were treated using the similar chemical concentration (0.2 to 0.5 M) of urea and calcium solution.



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Sustainable Biocement Production via Microbially Induced Calcium

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