Mathematical expressions of specifics substrate utilization rates for known kinetic models.
\r\n\t
",isbn:"978-1-83968-571-2",printIsbn:"978-1-83968-570-5",pdfIsbn:"978-1-83968-599-6",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,hash:"dd81bc60e806fddc63d1ae22da1c779a",bookSignature:"Dr. Sebahattin Demirkan and Dr. Irem Demirkan",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10818.jpg",keywords:"Decision Making, Blockchain, Accounting, Earnings Management, Strategic Alliances, Innovation, Performance, Corporate Governance, Accounting Quality, Digital Assets, Internationalization, MNCs",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"January 28th 2021",dateEndSecondStepPublish:"February 25th 2021",dateEndThirdStepPublish:"April 26th 2021",dateEndFourthStepPublish:"July 15th 2021",dateEndFifthStepPublish:"September 13th 2021",remainingDaysToSecondStep:"12 days",secondStepPassed:!0,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"Academician in the area of accounting who believes in the impact of interdisciplinary research. Dr. Sebahattin Demirkan's research interests are in the areas of financial accounting, capital markets, auditing, corporate governance, strategic alliances, taxation, CSR, and data analytics.",coeditorOneBiosketch:"Researcher of strategic management, corporate entrepreneurship, and international business; specific interests include innovation, the ambidexterity framework, inter-organizational relationships, and networks. Experienced in teaching graduate and undergraduate courses in strategy, entrepreneurship, and international business and management areas.",coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"336397",title:"Dr.",name:"Sebahattin",middleName:null,surname:"Demirkan",slug:"sebahattin-demirkan",fullName:"Sebahattin Demirkan",profilePictureURL:"https://mts.intechopen.com/storage/users/336397/images/system/336397.jpg",biography:"Dr. Sebahattin Demirkan is a Professor of Accounting. He earned his Ph.D. in Accounting/Management Science at Jindal School of Management of the University of Texas at Dallas where he got his MS in Accounting, MSA Supply Chain, and MBA degrees. He got his BA in Economics and Management at the Faculty of Economics and Administrative Sciences at Bogazici University, Istanbul. He worked at Koc Holding, a private venture capital firm, and the University of California, Berkeley during and after his education at Bogazici University. His research interests are in the areas of financial accounting, capital markets, auditing, corporate governance, strategic alliances, taxation, CSR, and data analytics. Dr. Sebahattin Demirkan has published articles in Contemporary Accounting Research, JAPP, JAAF, TEM, Journal of Management, and other top academic journals. He teaches several different classes in both undergraduate and graduate levels in Accounting and Analytics programs. He is a treasurer and vice president of the TASSA, board member of the BURCIN and member of the American Accounting Association.",institutionString:"Manhattan College",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Manhattan College",institutionURL:null,country:{name:"United States of America"}}}],coeditorOne:{id:"342242",title:"Dr.",name:"Irem",middleName:null,surname:"Demirkan",slug:"irem-demirkan",fullName:"Irem Demirkan",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000033HrA8QAK/Profile_Picture_1606729803873",biography:"Dr. Irem Demirkan earned her Ph.D. in International Management Studies and M.S. in Administrative Studies at Jindal School of Management at the University of Texas at Dallas, USA. She got her BA in Economics at the Faculty of Economics and Administrative Sciences at Bogazici University, Istanbul, Turkey. She worked in the finance and textile industries before joining to academia. Dr. Demirkan has published research in the areas of strategic management and corporate entrepreneurship in journals such as the Journal of Management, Journal of Business Research, Management Science, European Journal of Innovation and Management, IEEE Transactions on Engineering Management, among others. Dr. Demirkan currently teaches strategic management, entrepreneurship, and international business at Loyola University Maryland in Baltimore, MD.",institutionString:"Loyola University Maryland",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Loyola University Maryland",institutionURL:null,country:{name:"United States of America"}}},coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"7",title:"Business, Management and Economics",slug:"business-management-and-economics"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"301331",firstName:"Mia",lastName:"Vulovic",middleName:null,title:"Mrs.",imageUrl:"https://mts.intechopen.com/storage/users/301331/images/8498_n.jpg",email:"mia.v@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3621",title:"Silver Nanoparticles",subtitle:null,isOpenForSubmission:!1,hash:null,slug:"silver-nanoparticles",bookSignature:"David Pozo Perez",coverURL:"https://cdn.intechopen.com/books/images_new/3621.jpg",editedByType:"Edited by",editors:[{id:"6667",title:"Dr.",name:"David",surname:"Pozo",slug:"david-pozo",fullName:"David Pozo"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"54415",title:"Production of Biogas and Performance Evaluation of Ultrasonic Membrane Anaerobic System (UMAS) for Palm Oil Mill Effluent Treatment (POME)",doi:"10.5772/67602",slug:"production-of-biogas-and-performance-evaluation-of-ultrasonic-membrane-anaerobic-system-umas-for-pal",body:'\nThe palm oil industry has grown tremendously in the recent years and accounted for the largest percentage of oil and fats production in the world in 2011. Over the last few decades, the palm oil industry has been growing rapidly. Palm oil has risen to become the most produced and consumed vegetable oil in the world, widely used in food, cosmetic and hygienic products due to its affordable price, efficient production and high oxidative stability [1]. Palm oil is the most produced vegetable oil in the world with a global production of almost 60 million tons and a global vegetable oil market share of more than 35% by weight in 2015 as reported by Hansen et al. [2] and MPOB [3]. The industry continues to generate huge revenues for the producing countries. Accordingly, it is not surprising that the oil palm industry is expected to grow further in the coming years as shown in Figure 1.
Global consumption of palm oil from 1995/1996 to 2014/2015 (USDA, 2016) [4].
Over the long term, global palm oil demand shows an increasing trend as an expanding global population gives rise to increased consumption of palm-oil based products world consumption of palm oil [5]. [6] Stated that palm oil industries have been significantly contributing towards the economic growth and increase standard of living among the South East Asian countries. Nowadays, the global production and demand for palm oil are increasing rapidly where the plantations are spreading across Asia, Africa and Latin America. The five leading palm oil producing countries are Indonesia, Malaysia, Thailand, Colombia and Nigeria [7] as shown in Figure 2.
Palm oil production by country [10, 11].
The development of palm oil industry in Malaysia has turned into a phenomenal in which the area of plantation expanded from year to year. The country is experiencing a robust development in new oil palm plantations and palm oil mills. This commodity plays a significant role in the Malaysia economic growth [8]. Throughout the year, Malaysia is blessed with favorable weather conditions, which are advantageous for palm oil cultivation [9]. Thus, it is not surprising that the highest yields have been obtained from palms grown in this region, which is far from its natural habitat. Besides, the Malaysian palm oil industry has grown to become a very important agriculture‐based industry, where the country is today one of the world\'s leading producer and exporter of palm oil.
\nFigure 3 depicts the statistics production of palm oil superseded soybean oil from 13% in 1990 to 28% of total oil and fats production in 2011. This is because oil palm has higher annual oil yield per hectare than other oil seeds crops including soybean [11] and palm oil has a relatively lower price as compared to the major alternative vegetable oils [12]. POME is highly polluted wastewater if not treated properly; it causes a lot of environment issues. POME is a colloidal suspension of 95–96% water, 0.6–0.7% oil and 4–5% total solids including 2–4% suspended solids originating from mixture of a sterilizer condensate, separator sludge and hydrocyclone wastewater [13]. The conventional treatment technology of POME employed in most of the palm oil mills in Malaysia is the ponding system of biological treatment [14–16]. However, coping with the increasing production in most palm oil mills, the undersized biological treatment system is unable to cope with the increased volume of POME [17]. Thus, proper POME treatment is urgently needed to ensure the sustainable economic growth of palm oil industry in Malaysia besides protecting the environment. Several researchers have proposed other biological treatments.
World oil and fat production in 1990 and 2011 [3–5].
The treatment system includes aerated lagoon system [18], conventional anaerobic digester [19], anaerobic contact process [20], upflow anaerobic sludge blanket (UASB) reactor [17, 19], close tank digester [21], trickling filter, aerobic lagoon system [18], aerobic rotating biological contactor [19] and evaporation process [13].
\nThe main objective of this study was to evaluate the performance and kinetics of the new designed ultrasonic membrane anaerobic system (UMAS) in the treatment of palm oil mill effluent (POME) based on three models [22–24]. Table 1 shows mathematical expressions for specifics substrate utilization rate for three kinetic models (Monod, Contois, and Chen and Hashimoto).
Kinetic Model | Equation 1 | Equation 2 | |
---|---|---|---|
Monod | [22] | ||
Contois | [23] | ||
Chen & Hashimoto | [24] |
Mathematical expressions of specifics substrate utilization rates for known kinetic models.
In anaerobic degrading of POME, biogas is formed when microorganisms, especially bacteria, degrade organic material in the absence of oxygen. Biogas consists of 50–75% methane (CH4), 25–45% carbon dioxide (CO2) and small amounts of other gases [25–27]. A simplified schematic representation of anaerobic degradation of organic matter is given in Figure 4. The AD process can be subdivided into the following four phases, each requires its own characteristic group of microorganisms.
Process stages of anaerobic digestion [30].
The sequence of reactions involved in the mechanisms of AD is hydrolysis, acidogenesis, acetogenesis and methanogenesis [28]. Hydrolysis is conversion of nonsoluble biopolymers to soluble organic compounds. Acidogenesis is summarized as a conversion of soluble organic compounds to volatile fatty acids (VFA) and CO2 while acetogenesis is the conversion of VFAs to acetate and H2 [29]. Methanogenesis represents conversion of acetate and CO2 plus H2 to methane and carbon dioxide gas.
The raw POME was collected from a near local palm oil mill in Lebah Hillier, Kuantan, Malaysia. The raw POME was stored in a cold room at 4°C before use. Different dilutions of POME were prepared using tap water. The pH of the feed was adjusted to 7.0 using a 6 N NaOH solution.
A laboratory scale, with an effective 200‐L UMAS reactor (Figure 5), was used in this study. The UMAS reactor consists of a cross‐flow ultrafiltration membrane apparatus, a centrifugal pump and an anaerobic reactor. The total volume of the reactor was 200 L, and the working volume was 150 L. Six multifrequency ultrasonic transducers, operated at 25 KHz, are bonded to two sides of the tank chamber and connected to a Crest Genesis Generator (250 W, 25 KHz; Crest Ultrasonic, Trenton, NJ, USA). The maximum operating pressure on the membrane was 55 bars at 70 WC, and the pH ranged from 2 to 12.
Experimental setup.
The following parameters were analyzed: COD, BOD, pH, VSS and TSS.
\nMethane gas was determined by gas chromatography with a stainless steel column (200 × 0.3 cm) packed with active carbon (30–60 mesh) using thermal conductivity detection. For TSS, VSS, volatile fatty acids and alkalinity were determined according to the standard methods [31]. The COD was measured using a Hach colorimetric digestion method (Method # 8000, Hach Company, and Loveland, CO, USA). The MLSS and MLVSS were determined by drying the sample at 105 and 550 ± 50°C.
The steady‐state performance of ultrasonic membrane anaerobic system (UMAS) was evaluated under different influent COD concentrations (70,400–90,200 mg/l), hydraulic retention time (HRTs) (500.8–14.7 days) and OLR of 1.5–9.0 kg COD/m3/day (Table 2). In this study, the system was considered to have achieved steady state when the operating and control parameters were within ±10% of the average value. The produced biogas contained only CO2 and CH4, so the addition of sodium hydroxide solution (NaOH) to absorb CO2 effectively isolated methane gas (CH4). Table 2 depicts the results of the application of three known substrate utilization models.
Steady state (SS) | 1 | 2 | 3 | 4 | 5 | 6 |
---|---|---|---|---|---|---|
COD feed, mg/L | 70,400 | 73,478 | 76,200 | 83,570 | 86,700 | 90,200 |
COD permeate, mg/L | 1197 | 1617 | 3048 | 3343 | 4508 | 6494 |
Gas production (L/day) | 290 | 310 | 340 | 400 | 480 | 540 |
Total gas yield, L/g COD/day | 0.48 | 0.53 | 0.58 | 0.67 | 0.78 | 0.81 |
% Methane | 81 | 78.5 | 75.6 | 73.8 | 68.6 | 64.6 |
CH4 yield, l/g COD/day | 0.39 | 0.54 | 0.57 | 0.60 | 0.64 | 0.70 |
MLSS, mg/L | 13,800 | 12,400 | 13,400 | 14,800 | 17,648 | 22,600 |
MLVSS, mg/L | 10,269 | 10,751 | 11,765 | 13,320 | 15,530 | 20,159 |
% VSS | 74.41 | 86.70 | 87.80 | 90.00 | 88.00 | 89.20 |
HRT, day | 500.8 | 60.6 | 22.6 | 14.7 | 11.20 | 8.6 |
SRT, day | 300 | 250 | 180 | 30.5 | 20.30 | 15.80 |
OLR, kg COD/m3/day | 1.0 | 3.5 | 6.0 | 8.5 | 11.0 | 15 |
SSUR, kg COD/kg VSS/day | 0.164 | 0.195 | 0.252 | 0.263 | 0.294 | 0.314 |
SUR, kg COD/m3/day | 0.023 | 0.724 | 2.225 | 4.576 | 5.685 | 7.347 |
Percent COD removal (UMAS) | 98.3 | 97.8 | 96 | 96.0 | 94.8 | 92.8 |
Summary of results (SS: steady state).
The operating conditions for the ultrasonic membrane anaerobic system (UMAS) over the 500‐day experimental setup are given in Table 2. The performance evaluation of the integrated ultrasonic membrane anaerobic system (UMAS) was generated at different influent COD concentrations and hydraulic retention times (HRTs). Table 3 depicted and summarized the kinetic coefficients. For the system results at influent COD concentrations from 70,400 to 90,200 mg/l and pH (6.7–7.8), UMAS was performed well. The mixed liquor volatile suspended solids (MLVSSs) for the first steady state were 10,400 mg/l, whereas the mixed liquor suspended solids (MLSSs) were 13,800 mg/l, equivalent to 75.36% of the MLSS. This low result can be explained due the palm oil mill effluent wastewater contains very high suspended solids.
Model | Equation | |
---|---|---|
Monod | 99.6 | |
Contois | 99.1 | |
Chen & Hashimoto | 99.5 |
Summary of the three known substrate utilization models application.
The volatile suspended solid (VSS) fraction in the reactor at sixth steady state was increased to 89.20%. Results have shown that the long solid retention time (SRT) of UMAS facilitated the decomposition of the suspended solids and their subsequent conversion to methane (CH4); these findings found by Nagano et al. [32] and Abdurahman et al. [33]. At organic loading rate, OLR of 15 kg COD/m3/day, the system registered the highest influent of COD 90,200 mg/l at this stage; the UMAS achieved 92.8% COD removal. Figures 6–8 shown that UMAS can be applied and treat POME efficiently. Among the three models applied, the Monod and Chen and Hashimoto models performed better, shown that UMAS reactor performance should consider organic loading rates. These two models suggested that the predicted permeate COD concentration (S) is a function of influent COD concentration (So).
The Monod model.
The Contois model.
The Chen and Hashimoto model.
The percentage removal of COD by UMAS at various HRTs was shown in Figure 9. It was observed that COD removal efficiency increased as HRT increased from 8.6 to 500.8 days and it was in the range of 92.8–98.3%. It was found that this value higher than the 85% COD removal is observed for POME wastewater treatment using anaerobic fluidized bed reactors [34] and the 91.7–94.2% removal is observed for palm oil mill effluent wastewater treatment using membrane anaerobic system [35], and the 93.6–97.5% removal is observed for POME treatment using membrane anaerobic system [33]. Interestingly, it was found that there is no much difference in COD removal efficiency between HRTs of 500.8 days (98.3%) and 14.7 days (96.0%). On the other hand, the COD removal efficiency has declined at shorter hydraulic retention time; at HRT of 8.6 days, the COD removal efficiency was reduced to 92.8%. Table 2 results show that UMAS result might because of grown of volatile fatty acids inside the reactor. Usually, the hydraulic retention times were mainly effected by the ultrafiltration (UF) membrane influx rates, which directly determined the volume of influent (POME) that can be fed to the reactor.
COD removal efficiency of UMAS under steady‐state conditions with various hydraulic retention times.
The evaluated biokinetic coefficients based on COD basis by UMAS were analyzed as shown in Table 2.
\nThe kinetic coefficients were calculated and summarized in Table 3. The growth yield coefficient, Y, value ranges from 0.32 to 0.68 gm VSS/gm COD, specific microorganic decay rate, b, and maximum substrate utilization rate, K, ranges from 0.350 to 0.374 COD/g VSS.day. Figure 10 depicts the relationship between the substrate utilization rates (SUR) and the specific substrate utilization rate for COD with various hydraulic retention times. The HRTs range from 8.6 to 500.8 days. The biokinetic coefficients of growth yield, Y, and specific microorganic decay rate, b, were calculated from the slope and intercept as shown in Figures 11 and 12. The evaluated maximum specific biomass growth rates, μmax, range from 0.248 to 0.474 day−1.
The specific substrate utilization rate for COD with various hydraulic retention times.
Evaluation of the growth yield, Y, and the specific biomass decay rate, b.
Evaluation of the maximum specific substrate utilization and the saturation constant, K.
A semicontinuous operation was conducted to verify the performance of the integrated ultrasonic membrane anaerobic system (UMAS) throughout a different hydraulic retention times (HRTs) and influent COD concentrations. In this study, the influent COD concentration was increased from 70,400 to 90,200 mg/l (for the six steady states). Figure 13 illustrates the gas production rate and the methane content of the biogas. It was clear that the methane CH4 yield decreased with increasing OLRs. Methane gas contents were varied from 64.6 to 81%, and the methane yield was varied from 0.39 to 0.70 CH4/g COD/day. The decreased CH4 yield with increasing OLR was also noted in many previous studies [36–40]. One of the reasons might be that shorter HRT of the system contributed to more active methanogens that were washed out during the removal of effluent. The gas production has increased from 290 to 540 L per day during the study. Biogas production increased with increasing OLRs from 0.48 l/g COD/day at 1.0 kg COD/m3/day to 0.81 l/g COD/day at 15 kg COD/m3/day. These findings are in line with the results obtained from Refs. [41–43].
Gas production and methane content.
The kinetic performance of newly designed ultrasonic membrane anaerobic system (UMAS) was evaluated in the treatment of palm oil mill effluent (POME).
\nThe steady‐state performance of ultrasonic membrane anaerobic system (UMAS) was evaluated under different influent COD concentrations (70,400–90,200 mg/l), hydraulic retention times (HRTs) (500.8–14.7 days) and OLR of 1.5–9.0 kg COD/m3/day.
\nAmong the three models applied, the Monod and Chen and Hashimoto models performed better, shown that UMAS reactor performance should consider organic loading rates. These two models suggested that the predicted permeate COD concentration (S) is a function of influent COD concentration (So).
\nIt was observed that COD removal efficiency increased as HRT increased from 8.6 to 500.8 days, and it was in the range of 92.8–98.3%. The evaluated maximum specific biomass growth rates, μmax, range from 0.248 to 0.474 day−1.
\nIt was found that the methane CH4 yield decreased with increasing OLRs. Methane gas contents were varied from 64.6 to 81%, and the methane yield was varied from 0.39 to 0.70 CH4/g COD/day.
Looking into the last 20 years—since the classical publications from the Royal Society, ETC Group, OECD/Allianz, European Commission, Swiss Reinsurance, and studies and think tanks related to risks and uncertainties of nanotechnology [1, 2, 3, 4, 5, 6, 7]—without any doubt, we are now in a better position concerning risks (assessment, analysis, evaluation, management, communication, policies, monitoring, and treatment) and benefits of nanotechnologies. However, new nanomaterials and new nanoproducts are achieving several markets, and the global changes on the business environment—including, fast, small and short-term life enterprises, start-ups and spin-offs based on new technologies—underline the need of special attention from the society regarding safety and environmental issues. Sometimes, in the nanotechnology business endeavor, low capital and poor-trained people without enough knowledge and guidance about safety, health and environmental regulations, standards and protocols could exposure, unnecessarily, workers, consumers and the environment.
\nFrom public and private investments, thousands of publications, research efforts, and scientific projects (money, time, and minds) have been done and much more should be done to follow the rapid technological and scientific development of nanoscience and its applications.
\nThe knowledge of bio and physicochemical interactions between nanomaterials and living organisms, the understanding of life cycle analysis (LCA) of nanomaterials on environment, and the time-related effects of chronic dose-response toxicity are key points that should be taken in account during the debate and to improve the safety approach of nanotechnological development.
\nRisk assessment and management of health, safety, and environmental (HSE) nanotechnology are very important aspects to mitigate risks and improve the benefits and transform opportunities into technological development on medical applications (cancer treatment, tissue engineering, diagnosis of diseases, DNA manipulation, etc.), flexible and communication devices, portable energy, food conservation, agriculture productivity and pest control, and countless new applications and uses.
\nCarbon is one of the most import elements on Earth. Carbon nanomaterials are changing the technology of XXI century, and its fundamental electronic and hybridization states transform it into one of the most remarkable chemical elements with applications from regenerative medicine to rocket capsules and flexible electronic devices.
\nCarbon hybridization states with sp3 and sp2 bonding system ally with the allotropy of carbon materials that produces soft, hard, light, and dense materials. The carbon use and applications came from charcoal for heating, passed by nuclear reactors to carbon-carbon composites used on new aircrafts or space capsules. However, after the discovery of fullerenes from Curt et al. [9, 10] and discovery of graphene by Geim and Novoselov [11], the research of carbon nanomaterials has been expanding in an unimaginable way [8, 9, 10, 11]. Figure 1 shows the carbon allotropes with special attention on nanoforms.
\nCarbon allotropes family (adapted from Ref. [12]).
The hybridization states of carbons allow then to assume different geometries in the space from 0D dimension (fullerenes, carbon dots) to 1D fiber type materials with high aspect ratio, passing by 2D flat material (graphene) to high complex 3D material such graphite, diamond, or schwarzite materials.
\nWhy we should think differently about health, safety, and environment when dealing with nanomaterials or nanoobjects? Nanotechnology has defined areas of science that take place at nanoscale (1–100 nm) [13, 14]. Many specific and fundamental aspects are related to HSE, including surface energy, functionability, and size. Figure 2 shows the main nanoparticle properties and how they are related regarding toxicological and risk assessment of nanomaterials. Those properties and the relation between them can be considered main aspects that should be considered to asses specific nanoparticle’s risks.
\nMajor relationships between properties and risk/toxicological interactions (adapted from Ref. [15]).
Size (distribution), shape, surface area, chemical composition/crystalline structure, and solubility are very important properties regarding the risk assessment of carbon nanomaterials [15].
\nThese properties can be assessed using different analytical tools. Table 1 shows the nanomaterial properties, the main characterization techniques, and also the degree of importance on the knowledge of such property for a risk assessment point of view.
\nNanomaterial properties | \nImportance | \nMain analytical characterization techniques | \n
---|---|---|
Chemical composition, structure and crystalline phase | \nExtreme | \nXRD, XRF, ICP-AES, AAS, HPLC, SIMS, MALD-TOF, EDS | \n
Specific surface area (density, porosity, and reactivity: flammability and explosivity) | \nExtreme | \nMultimolecular gas adsorption (BET/adsorption isotherm method), gas (He) pycnometer, mercury intrusion porosimetry (MIP) | \n
Shape dimensionality/morphology (0D, 1D, 2D, or 3D), number of layers | \nExtreme | \nTEM, XRD, SEM, Raman | \n
Stiffness (rigid and flexibility, aspect ratio) | \nHigh-medium | \nMicroscopy (SEM, TEM, …), XRD | \n
Solubility (dissolution and toxicant species) release | \nExtreme | \nTables of solubility, Hildebrand and Hasen parameters | \n
Surface species: R(O-N)S: reactive (oxygen and nitrogen) species, C/O atomic ration, etc. | \nHigh-medium | \nXPS, FTIR, NBT test, ESR, EPR | \n
Surface chemistry (functionality, hydrophobicity and hydrophilicity, and adsorbed compounds and groups) | \nHigh-medium | \nOxygen singlet analysis, XPS, FTIR, pH, contact angle microscopy, AES, EELS, DTA | \n
Size and size distribution (aerodynamic, hydrodynamic) | \nExtreme | \nSEM, DLS, FCS, XRD | \n
Solid bonding energy and type | \nMedium-low | \nDSC-TGA, simulation (first principles) | \n
Surface charge density | \nMedium | \nSPM, PCM, SPR | \n
Surface speciation | \nMedium-low | \nXPS, FTIR, NMR | \n
Agglomeration and aggregation state | \nHigh-medium | \nXRD, SEM | \n
Surface nanoparticle-protein corona | \nMedium | \nSimulation, electrophoresis | \n
Bio-(persistence, accumulation, degradation and digestibility), endotoxin content | \nHigh-medium | \nSpecific corrosion, digestibility, chemical analysis, LAL, TET, TNF, etc. | \n
Structural atomic defects, ordering, and faceting | \nMedium-low | \nMicroscopy (TEM, SEM), XRD, Raman | \n
Quantum, electric and magnetic properties | \nUnder evaluation | \nInduced magnetization, Currie balance | \n
Concentration (mass, number of particles/fibers): property of area: environment, workplace, office, etc. | \nExtreme | \nOPC, CPC, light-scattering photometer, gravimetric analysis, etc. | \n
Nanomaterial evaluation: main relevant properties related to risk assessment and usual material characterization techniques [16, 17, 18, 19, 20].
Legend: XPS: X-ray photoelectron spectroscopy, XRD: X-ray diffraction, XRF: X-ray fluorescence, OPC: optical particle counter, CPC: condensation particle counter, FTIR: Fourier-transform infrared spectroscopy, NMR: nuclear magnetic resonance, ICP: inductively coupled plasma, AA: atomic absorption spectroscopy, HPLC: high-performance liquid chromatography, ESR: electron spin resonance, DLS: dynamic light scatter, EDS: X-ray energy dispersive spectroscopy, AES: Auger electron spectroscopy, TGA: thermogravimetric analysis, LAL: Limulus amoebocyte lysate, FCS: fluorescence correlation spectroscopy, EPR: electron paramagnetic resonance, TEM: transmission electron microscopy, SEM: scanning electron microscopy, BET: Brunauer-Emmett-Teller, pH: hydrogen-ion activity, OES: optical emission spectroscopy, SPM: single potentiometric method, PCM: potentiometric conductometric method, SPR: surface plasmon resonance, FP: first principles, MIP: mercury intrusion porosimetry, NBT: nitroblue tetrazolium test, MALD-TOF: matrix-assisted laser, desorption/ionization-time of flight, EELS: electron energy loss spectroscopy, and TET: TNF-α expression test (where: TNF is tumor necrosis factor).
It is noticed that the concentration of nanomaterial could be described using different metrics such as mass/volume or number of particulates (or fibers)/volume. Concentration, type/chemical, and physical state, in general, are the most important technical aspects related to HSE management of workplace under evaluation.
\nA careful analysis on nanomaterial’s processes such as handling, storage, manipulation, production, and incorporation are essential to determine exposure routes and to identify possible emission procedures or other safety aspects. Figure 3 details the possible relations between biokinectics and pathways for nanoparticles exposure route and translocation .
\nBiokinectics of nanoparticles related to exposure routes, uptake pathways, translocation/distribution and excretory pathways of NP (adapted from Ref. [21]).
The interaction between nanoparticles and cells is important to determine health surveillance (target organs and excretory pathways) and the possible damage mechanics and effects related to nanotoxicity such as physical damage of lysosomes, lipid peroxidation in vesicles, DNA damage of cellular nucleus, mitochondrial damage of cell mitochondria, protein misfolding on Golgi apparatus, and cellular membrane damage from oxidative stress, surfactant interaction, membrane damage by ions, and disruption of cell membranes [22]. Then, new properties from nanosized effects (high area and energy, specific functionalization and quantum effects) provide different biological, physical, and/or ecological effects, turning risk assessment and evaluation more complex, sometimes more specific and time-consuming.
\nOccupational exposure routes are intimately related to physical state of nanoparticles from processing methods (synthesis), processing equipment, workplace design, pollution-control equipment, handling steps, and operational procedures. Mainly, dispersion and inhalation are the main exposure contamination route. HEPA class filter are very efficient to control the number of nanoparticles disperse on air (>99.97%), while ULPA class filters have at least 99.995% of efficiency [22]. Use of a proper project design of air filtration is one of most important stages to avoid personal and environmental contamination. Table 2 shows the typical HEPA and ULPA filter specifications based on ISO 1822:2009 (*) and the principal four primary mechanisms of filter particle collection [23]. The use of clean rooms or lamellar flow chamber or environmental/gas-controlled glove box could be applied to contain particulates during the handling of nanomaterials [24]. Personal protective equipment (PPE) also uses HEPA filtration on mask or coupled filtration devices. Main aspects of contamination and failure to prevent contamination regarding filtration masks came from poor personal training to fix and use masks and the incorrect size and face matches (respiration facepiece and face). A chartered safety and health practitioner’s evaluation based on work activities, operational procedures, workplace environment, nanoparticulate type/chemical concentration, and respirator fit factor should be applied according to occupational standards and guides [25, 26, 27].
\nHEPA and ULPA filters’ retention characteristics.
The second most important exposure route of nanoparticles is from deposition or contact with skin. Usually, “perfect” skins without damages, cuts, or scratches work as barrier against nanoparticle penetration. However, the adequate gloves’ and protective clothes’ (made by high-density polyethylene fibers) specification should take in care several parameters such as glove material’s chemical resistance compatibility [28], glove thickness, type/time of glove use (disposable/unsupported), temperature of use, type of labor activity and type, concentration, and agglomeration state of nanoparticles regarding the nanoparticle penetration behavior [29].
\nThe material safety data sheets (MSDS) have essential information’s and, regularly, they are used during the risk assessment and in workplaces as safe procedures for hazardous chemicals and its mixtures. The SDS enable anticipation, evaluation, recognition, and control of workplace exposures and environmental hazards [30, 31]. The major problem of SDS of nanomaterials is the lack of information and/or wrong use of “bulk material” properties instead of nano. Evaluation of nano-SDS indicated that 35% of the sheets are unreliable [32]. About this issue, American Industrial Hygiene Association (AIHA) has a program that recognizes chemical hazard communication and environmental health professionals who specializes in authoring safety data sheets and labels [33]. Recently, SECO, a Swiss State Secretariat for Economic Affairs (SECO), published a guideline and two examples of synthetic nanomaterial’s SDS [34, 35].
\nThe knowledge of nanomaterial (quantitative) structure-activity relationships (Q)SAR is another important point of HSE evaluation during the risk assessment. Validated endpoints could explicate more clearly when a nanomaterial would be classified as “toxic” or “nontoxic” in particular exposure conditions providing more analytical, rational, and explicit data interpretation. Table 3 shows the most common endpoints based on OECD test guidelines for nanomaterials and the UN-GHS. Notice that the UN-CGH for chemicals (including nanosized) just shows the parameter, while the OECD guideline could indicate and classify them [36, 37].
\n\n | OEDC (nano) | \nUN-CGH (chemicals) | \n
---|---|---|
Physicochemical properties | \nMelting point, boiling point, vapor pressure, K octanol/water, K organic/C/water*, water solubility | \nAppearance (physical state, color, etc.), upper/lower flammability or explosive limits, odor, vapor pressure, odor threshold vapor density, pH, relative density, melting point/freezing point, solubility(ies), initial boiling point and boiling range, flash point, evaporation rate, flammability (solid, gas), partition coefficient: n-octanol/water, auto-ignition temperature, decomposition temperature, and viscosity. | \n
Environmental fate | \nBiodegradation, hydrolysis, atmospheric oxidation, bioaccumulation* | \n(Nonmandatory): \n
| \n
Ecological effects | \nAcute fish toxicity, acute Daphnia toxicity, alga toxicity, long-term aquatic toxicity, terrestrial effects | \n(Nonmandatory): \n
| \n
Human health effects | \nAcute oral toxicity, acute inhalation toxicity | \nInformation on the likely routes of exposure (inhalation, ingestion, skin, and eye contact). The SDS should indicate if the information is unknown: description of the delayed, immediate, or chronic effects from short- and long-term exposures. The numerical measures of toxicity (e.g., acute toxicity estimates such as the LD50 (median lethal dose)) − the estimated amount [of a substance] expected to kill 50% of test animals in a single dose. Description of the symptoms. This description includes the symptoms associated with exposure to the chemical including symptoms from the lowest to the most severe exposure. Indication of whether the chemical is listed in the National Toxicology Program (NTP) Report on Carcinogens (latest edition) or has been found to be a potential carcinogen in the International Agency for Research on Cancer (IARC) Monographs (latest editions) or found to be a potential carcinogen by OSHA. | \n
Akin irritation/corrosion | \n||
Eye irritation/corrosion | \n||
Repeated dose | \n||
Genotoxicity (in vitro) | \n||
Genotoxicity (in vitro, nonbacterial) | \n||
Genotoxicity (in vivo) | \n||
Reproductive toxicity | \n||
Developmental toxicity | \n||
Carcinogenicity* | \n||
Organ toxicity | \n||
(hepatotoxicity, cardiotoxicity, nephrotoxicity, etc.). | \n
OECD endpoint test guidelines for nanomaterials and MSDS (material safety data sheet) parameter.
Non-screening information data set (SIDS) endpoints.
From UN-GHS (classification and labeling of chemicals of UN-globally harmonized system).
Remark: the US National Cancer Institute published on this website several assays that have been standardized to work with a variety of nanomaterials. Information available at [38].
Risk assessment could be defined when risk analysis and risk evaluation are carried in a joint process [39]. Health Safety Executive from the United Kingdom (HSE-UK) uses a simple five-step risk assessment based on the following topics:
Identify the hazard.
Decide who might be harmed and how.
Evaluate the risks and decide on precautions.
Record your findings and implement them.
Review your assessment and update if necessary.
The application of this kind of assessment can be useful; however, it needs some adjustments due to uncertainties and lack of information (e.g., long-term or chronic evaluation of nanomaterials exposure), new materials without completed toxicological effects/studies or accurate dose-response database (OEL—occupational exposure limits, TLV—threshold limit values, OSHA/PEL—occupational safety and health administration-permissible exposure limits, WEEL—workplace environmental exposure level, NIOSH/PEL—National Institute for Occupational Safety and Health-recommended exposure limit, IOELV—indicative occupational exposure limit value, etc.) [40].
\nThe availability of occupational and epidemiological data for chemicals and nanomaterials is a key aspect of risk assessment. The amount of new chemicals produced and released on the market is huge and huge means a hundred thousand per year. Based on Chemical Abstract Services (CAS) registry (a division of American Chemical Society), since 1800s, more than 145 million organic and inorganic substances were disclosed in the literature [41], while the publication 2018 TLV and BEIs from the American Conference of Governmental Industrial Hygienists (ACGIH) presents around 700 chemicals with TLV-STEL or TLV-TWA values (short-term exposure limit and time-weighted average, over the 8-hour working day). At the nanoworld, only 56 nanomanufactured materials have occupational exposure limit (OEL) proposed values [42]. Table 4 presents some of the proposed exposure limit values for carbon nanomaterials. The suggested values vary enormously, and no consensus exists between the authors.
\nTypes of nanocarbons | \nExposure | \nReference | \n
---|---|---|
Multiwalled carbon nanotubes (MWCNT) | \nNo effect concentration in air <2.5 μg/m3 | \nLuizi, 2009 (from Nanocyl) | \n
Multiwalled carbon nanotubes (MWCNT) | \nOccupational exposure limit (OEL) < 50 μg/m3 for 8-hour TWA during a 40-hour workweek | \nPauluhn, 2010 (from Bayer) | \n
Fullerenes (C60) | \nIndicative no-effect level (INEL) < 7.4 μg/cm3 | \nAschberger, 2011 | \n
Multiwalled carbon nanotubes (MWCNT) 10 nm | \nIndicative no-effect level (INEL) < 1.0 μg/cm3 | \nAschberger, 2011 | \n
Carbon nanotubes (CNTs) | \nProposed nanoreference values (NRV) < 0.01 fibers/cm3 | \nvan Broekhuizen, 2012 | \n
Carbon nanotubes (CNTs) | \nRecommended exposure limit (REL) < 1.0 𝜇g/m3 for 8-hour TWA during a 40-hour workweek | \nNIOSH, 2013 [64] | \n
Carbon nanofibers (CNFs) | \nOccupational exposure limit (OEL) <0.01 fibers/cm3 | \nStockmann-Juvala, 2014 | \n
Carbon nanotube group, SWCNT, DWCNT, MWCNT | \nOccupational exposure limit (OEL) < 30 μg/m3 for 8-hour TWA during a 40-hour workweek | \nNakanishi, 2015 | \n
Proposed exposure limit values for carbon nanomaterials.
In this scenario, the adoption of a precautionary posture should be the only option. In its strict form, the precautionary principle “requires inaction when action might pose a risk,” or in an active form, “it requires to choose the less risky alternatives when they are available, and for taking responsibility for potential risks” [43, 44, 45]. This should be adopted and carefully evaluated on control of risks (identification, evaluation, elimination, mitigation, monitoring, and communication) and on the choice of mitigation procedures when dealing with nanomaterials. The adoption of a hierarch for health and safety controls should be mandatory. Figure 4 shows health, safety, and environmental hierarchy controls in a schematic representation.
\nHSE hierarchy controls (adapted from Ref. [46, 47]).
The most effective control is the elimination of the hazard, and the less effective is the use of protective equipment. The viability to apply each type should be analyzed, case-by-case, considering the identified risks and its classification.
\nThe risk management of nanomaterials nano-objects, aggregates and agglomerates (NOAA) could be based on international standards like ISO 31000 [48] and should be incorporated in the quality, health, safety, and environmental system management. Adaptations for the correct use of risk assessment tools to deal with specificities and specific properties of nanomaterials are necessary [49, 50]. Figure 5 shows the core points of risk management and several tools that could be used to facilitate the understanding and the day-by-day procedures.
\nRisk management of NOAA’s topics of risk identification, analysis, evaluation, treatment, and communication.
The applying of safety aspects in early stage of projects involving nanomaterials is fundamental to mitigate risks and improve the quality (robustness) of HSE system. The CDC/NIOSH guide from Nanotechnology Research Center (NTRC): “Controlling Health Hazards When Working with Nanomaterials: Questions to Ask Before You Start” is a very good starting point to deal with nanomaterials in a safe manner [51]. Table 5 shows major protocols, standards, and guidance on the safe manipulation of NOAAs.
\nOrganization (acronym)/country and website | \n
---|
IRSST (Canada), Institut de recherche Robert-Sauve en sante et en securite du travail/ | \n
ILO/ONU (International Labour Office-Swiss)/ | \n
CDC-NIOSH and OSHA (USA), Centers for Disease Control and Prevention—The National Institute for Occupational Safety and Health/ Occupational Safety and Health Administration/ | \n
Cordis (Europe), Community Research and Development Information Service/ | \n
SWA (Australia), Safe Work Australia/ | \n
ISO (Switzerland), International Organization for Standardization/ | \n
HSE (UK), Health and Safety Executive/ | \n
BAuA (Germany), German Federal Institute for Occupational Safety and Health/ | \n
DTU (Denmark), Danish Ecological Council and Danish Consumer Council/ | \n
ANSES (France), Agence Nationale de Securite Sanitaire de l’alimentation/ | \n
AIST (Japan), National Institute of Advanced Industrial Science and Technology/ | \n
OECD (France), The Organization for Economic Co-operation and Development/ | \n
RIVM (Holland), Dutch National Institute for Public Health and the Environment/ | \n
ABDI (Brazil), Brazilian Agency for Industrial Development/ | \n
EUON (Europe), European Union Observatory for Nanomaterials/ | \n
Major protocols, standards, and guidelines on the safe handling of nanomaterials and the risks associated with nanoparticles available from different organizations [52].
Due to lack of exposure limits and lack of information concerning toxicological effects of nanomaterials (in general and carbon nanomaterials specifically), the use of risk assessment based on control banding has been widely applied. Several tools based on this concept are available as shown in Table 6.
\nTool | \nWeb address | \nCountry | \n
---|---|---|
CB Nanotool | \n\n | \nUSA | \n
IVAM Guidance | \n\n | \nHolland | \n
Swiss Precautionary Matrix | \n\n | \nSwiss | \n
Stoffenmanager Nano | \n\n | \nNederland | \n
ANSES CB Tool | \n\n | \nFrance | \n
NanoSafer CB | \n\n | \nDenmark | \n
NCBRA—Nanomaterial Control Banding Risk Assessment | \n\n | \nAustralia | \n
CBG—Control Banding Guideline | \n\n | \nCanada | \n
Major risk assessment tools based on control banding and risk matrices ([53] and Google searching tool).
Along with all carbon nanomaterial developmental stages—from laboratory to industrial scale operations—different routes can lead to environmental emissions. Decision making related to waste disposal and control actions to avoid (or allow) air and water emissions should be taken in the early stages, prior to the enhancement of production scales. These types of decision will also be needed after the use phase of the nano-enabled products. Naturally, through several possible paths, different environment compartments will interact (or better, are interacting) with carbon nanoparticles.
\nDepending on the scale, type of synthesis route, and activity, carbon nanoparticle emissions to the atmosphere can occur in larger or smaller amounts. As mentioned, exposition via inhalation is the main concern in the field since several authors have reported possible effects and damage to the respiratory system [18, 54]. In this sense, important precautionary actions comprise the establishment of emission control strategies and exposure monitoring.
\nNanoparticles in the air were traditionally referred to ultrafine particles [55]. Main processes can occur with these particles in the air: photochemical reactions, agglomeration, and deposition. The deposition depends on the gravitational settling velocity, which is proportional to the diameter of the particle—smaller nanoparticles in the air will deposit at a much slower rate than larger particles [56, 57]. It is possible to assume that the particle diffusion in the atmosphere is governed by Brownian motion, being the diffusion rate inversely proportional to the particle diameter. In that sense, it is possible to assume that “aerosolized” nanoparticles in an agglomerate form, even at a low mass concentration, will be deposited at a faster rate than larger particles [56, 57, 58].
\nAlso, the specific properties of the nanomaterial such as surface charge, aspect ratio, and presence of functional groups or other molecules in the nanoparticle surface will play a significant role in the atmospheric processes, interfering in the photochemical reactions, agglomeration, and deposition. The behavior of these particles in the air is a complex and dynamic process.
\nBeing detected the risk of a carbon nanomaterial becoming airborne, some control measures should be taken. Handling nanomaterials should be performed in a closed system, for instance, a glove box. If activities outside a closed system cannot be avoided, as during refilling or filling, dust should be extracted at the source, using exhaustion devices (like flexible air ducts). It is recommended by several agencies to use HEPA filters of class “H14” in safety cabinets or other exhaustion fume hoods at the workplace. The use of safety cabinets and microbiological safety cabinets, which recirculate air from the cabinet interiors, through a HEPA filter, back into the laboratory, can be used for small quantities of carbon nanomaterials in the absence of hazardous vapors or gases. The filter must be HEPA, and charcoal filters alone must not be used in this case. Also, suitable protective measures to avoid energetic processes that might generate airborne dusts or aerosols and the immediate sealing of bottles/vessels after use are simple and effective actions [22, 23, 24, 25, 26].
\nDifferent methods can be used for measuring airborne nanomaterials. As illustrated in Figure 6, atmospheric particulate matter can be analyzed through different methods using passive or active sampling methodologies.
\nFlowchart of methods for measuring airborne nanomaterials.
Online measurement methods are equipment-based measurements with low response time, giving in real time, the concentration of particles and nanoparticles in the air. Normally, it is a general measurement that cannot distinguish the type of nanomaterial (related to its composition or morphology) being analyzed. As for the carbon nanomaterials, the morphology is a differential property; the simple measurement of concentration cannot determine the presence of the nanomaterial in the air. Recently, more relevant indicators have emerged for describing nanoparticle aerosols, including particle number, surface and mass concentrations, and criteria relating to their size or optical properties (Raman-based equipment) [59, 60].
\nOff-line methods allow quantitative determination (by mass), and the identification of the type of nanomaterial, however, requires long-term sampling and the sampling equipment is often expensive. Since these methods comprise sample collection, the advantage is the possibility to analyze the air-collecting filters in order to determine the composition and to verify the presence of carbon nanoparticles in the filter. The complexity of these samples in terms of composition and the likely presence of other carbonaceous materials (amorphous carbon from diesel combustion, for instance) is a special challenge related to the air monitoring of carbon nanoparticles. It is important to say that quantification is another difficult task. Carbon nanoparticles are very light, and the gravimetric method gives a result related to the total particulate sampled. A recent study analyzed the use of thermogravimetric analyses in order to detect and differentiate different types of nanocarbon directly in the air-collecting filter [61]. For the off-line gravimetric method, conventional sampling regulations such as NIOSH Method 5040, NIOSH 0500, and NIOSH 0600 can be used [62, 63].
\nPassive methods are related to the natural deposition of those particles in different substrates (TEM grids, silica, holey carbon tapes) aiming to visualize its presence using an electron microscope. Although it allows identification of the carbon nanomaterial and its morphology, it is an expensive and time-consuming method. Also, the uncertainties related to the behavior of these particles in the air make it difficult to assume the time needed for its deposition and settling in those substrates.
\nGraphene and carbon nanotube water dispersions are a market reality. Although the fact of being, originally, insoluble materials, the possibility to have water dispersions containing carbon nanomaterials is often considered, since the delivery of a product in a liquid media can allow its use for different application purposes.
\nDifferent types of liquids containing carbon nanomaterials can be generated in research and (pre) industrial facilities. The use of acids and surfactants in synthesis and functionalization routes are common and, therefore, will be components of the produced liquid waste. Besides the nanomaterial, the presence of other substances must be evaluated since the knowledge of their own risk and best disposal practice must be considered.
\nCarbon nanoparticles may interact with aquatic systems by sewer discharges, or indirectly, coming from soils during the solid nanomaterial (or products containing the nanomaterial) disposal in landfills.
\nIt is unlikely that public water treatment systems will be able to remove those particles from the influent. Specific properties such as surface charge and the presence of surfactants are some of the difficulties related to the removal of these nanomaterials in a general way [65, 66]. In some cases, at higher efficiency regime, the nanomaterials are removed from the influent and adsorbed into the sludge that will be disposed in the soil [67].
\nWhile there are no specific rules that regulate the disposal of nanomaterials in the environment, it is necessary to create a precautionary strategy for the best environmental management.
\nA possible approach is the treatment of the liquid nanowaste, aiming the removal of the nanoparticles from the water and its possible reuse in the production process. Liquid waste treatment processes are established in the industry, making possible a similar development in the nanotechnology field. The tendency of some nanocarbons, like graphene nanosheets, to aggregate and form a precipitated agglomerated due to 𝜋−𝜋 staking interactions, can facilitate this separation [68]. On the other hand, graphene nanosheets with attached metal nanoparticles easily aggregate in the presence of ions [66]. The treatment and recycling are strict approaches that eliminate the risk of any possible harmful effects to aquatic systems, since the nanoparticle will not reach the environment. Although it seems an interesting choice, the establishment of treatment/recycling routes will require research and development efforts, involving nontrivial issues related to characterization of nanocarbon on complex matrices and a clear understanding of key nanomaterial properties.
\nBesides the challenge of such approach, it has clear advantages since it adds to the nanomaterial development of a safe-by-design practice in accordance with sustainable principles, therefore creating the possibility of specific solutions for each case. A process to recover single-walled carbon nanotube anode from battery anodes [69] and the use of serpentine to treat waste graphene were already reported [70] as examples of recycling the nanocarbons used in specific applications. It is a complex subject with an urgent need for recycling and end-of-life (EOL) studies. Specifically, the generation of the nonproduct outputs in nanocarbon production process is common [71]. The industrial scale production highlights this need: the projected global annual production of carbon-based nanocarbons was in order of a few hundred tons in 2001 and estimates 58,000 tons annually to 2020 [72].
\nAccording to several recommendations [73, 74, 75, 76], the incineration is another method to treat these types of waste. These recommendations are based on the precautionary principle, and independent of the amount, the presence of nanomaterials in liquids that should be discarded lead to its classification as hazardous wastes.The Organization for Economic Co-operation and Development (OECD) [74], in 2013, published a document providing an overview of scientific findings on the behavior and exposure of engineered nanomaterials (ENMs) during the waste incineration process in order to identify knowledge-gaps regarding specific aspects of the disposal of waste containing nanomaterials (WCNMs). According with this document, all waste incineration plants should be equipped with a flue gas treatment system as, for instance, described in the European Union BREF document (Integrated Pollution Prevention and Control—Reference Document on the best available techniques for Waste Incineration, August 2006). Until today, there are still a large number of waste incineration plants worldwide that do not have adequate flue gas treatment systems. In addition, the treatment and disposal of solid residues from waste incineration also require further research that should include the determination of conditions that enable the efficient removal of nanocarbons from the solid waste. Each material needs to be evaluated in an individual way. Decomposition temperatures depend on the nanomaterial-specific properties: size, shape, degree of defects, and presence or not of functional groups can interfere on it.
\nBesides the liquids containing nanocarbons, solid wastes are also generated in research facilities and in industrial settings producing or working with carbon nanomaterials. In terms of risk management, an important question regarding the form of the nanomaterial in the solid waste: Is it bound in a matrix or free in a powder form? The classification of the types of solid and liquid wastes is a fundamental step. A careful look in the processes and the development (and clear communication) of disposal practices are essential to avoid unnecessary emissions to the atmosphere or the disposal of a solid nanomaterial, in powder form in landfill soil.
\nLandfill waste disposal of carbon nanomaterials leavings derived from production facilities and from nano-enabled products are relevant routes leading to the soil environment. Another possibility is the use of nanoproducts directly in the soil for agricultural and construction purposes—cement containing carbon nanotubes is a well-studied application [77].
\nProgress in nanowaste management also requires studies on the environmental impact of these new materials. Knowing that several parameters must be evaluated when assessing the risk—such as the amount of nanomaterial to be discarded and its singular properties—there is a preponderant factor: the complexity of the natural environment, which makes it difficult to carry out systematic studies for the identification of the risk. Studies focusing the identification of the harmful effects of these nanomaterials in realistic scenarios are rare. Works modeling the flows of engineered nanomaterials during waste handling are the important ways to support this lack of information [78, 79].
\nNowadays, the amount of information of HSE of nanomaterials including the new nanocarbons is still not completed; however, the correct use of risk assessment and risk analysis tools based on a precautionary vision could mitigate risks and control the exposure at workplaces. Improving the quality and ratability information of SDS and improving the grouping of nanomaterials by risk classes based on properties and biological effects must be a continuous work. A multidisciplinary environmental assessment and use of LCA tools to nanomaterials must be continued, improving risk models and taking care of epidemiological aspects of human and environmental interaction with manmade nanoparticles.
\nAuthors would like to thank the MGgrafeno project, a joint initiative of Codemig, Center for Development of Nuclear Technology (CDTN) and Federal University of Minas Gerais (UFMG).
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\\n\\nIntechOpen has collaborated with Enago, through its sister company, Ulatus – one of the world’s leading providers of book translation services. The services are designed to convey the essence of your work seamlessly to readers from across the globe in their own language. Enago’s expert translators incorporate cultural nuances in translations to make the content relevant for local audiences while retaining the original meaning and style. With a high degree of linguistic and subject expertise, Enago translators are equipped to handle all complex and multiple overlapping themes encompassed in a single book to deliver a superior quality of translation.
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\n\nBENEFITS
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\n\nSee a complete overview and description of the steps involved in the publishing process here.
\n\nSEND YOUR PROPOSAL
\n\nIf you are interested in publishing your book with IntechOpen, please submit your book proposal by completing the Publishing Proposal Form.
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