Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil and Iowa State University Compost Rows

In this study the degradation of polylactic acid (PLA) plastic films in Costa Rican soil and in a leaf composting environment was investigated. Three types of PLA films were used: Ch-I, (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC). The average soil temperature and moisture content in Costa Rica were 27°C and 80%, respectively. The average degradation rate of PLA plastic films in the soil of the banana field was 7675 M _w/week. Two compost rows were set up at the Iowa State University (ISU) (Ames) compost site. Temperature and relative humidity of the compost rows were kept at 55 ± 5°C and 50 ± 10% RH, respectively. The degradation rates of GII and Ca-I in the compost rows were 113,290 and 71,283 M _w/week, respectively. Therefore, it was estimated that in Costa Rican soil and in compost rows, PLA would be visibly degraded in 6 months and in 3 weeks, respectively.     

Biodegradability of chitin- and chitosan-containing films in soil environment

The biodegradation of polyethylene-chitin (PE-chitin) and polyethylene-chitosan (PE-chitosan) films, containing 10% by weight chitin or chitosan, by pure microbial cultures and in a soil environment was studied. Three soil-inhabited organsims,Serratia marcescens, Pseudomonas aeruginosa, andBeauveria bassiana were able to utilize chitin and chitosan in prepared PE-chitin and PE-chitosan films after eight weeks of incubation at 25°C in a basal medium containing no source of carbon or nitrogen. In a soil environment, the biodegradation of those films was studied and compared with a commercial biodegradable film containing 6% by the weight of corn starch. In soil placed in the lab, 73.4% of the chitosan and 84.7% of the chitin in the films were degraded, while 46.5% of the starch in the commercial film was degraded after six months of incubation. In an open field, 100% of the chitin and 100% of the chitosan in the films were degraded, but only 85% of the starch in the commercial film was degraded after six months of incubation. The weight of controls, (polyethylene films), remained mainly stable during the incubation period. Both PE-chitin and PE-chitosan films degraded at a higher rate than the commercial starch-based film in a soil environment indicating the potential use of chitin-based films for the manufacturing of biodegradable packaging materials.     

Biodegradation of Injection Molded Starch-Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Blends in a Natural Compost Environment

Injection molded specimens were prepared by blending poly (hydroxybutyrate-co-valerate) (PHBV) with cornstarch. Blended formulations incorporated 30% or 50% starch in the presence or absence of poly-(ethylene oxide) (PEO), which enhances the adherence of starch granules to PHBV. These formulations were evaluated for their biodegradability in natural compost by measuring changes in physical and chemical properties over a period of 125 days. The degradation of plastic material, as evidenced by weight loss and deterioration in tensile properties, correlated with the amount of starch present in the blends (neat PHBV < 30% starch < 50% starch). Incorporation of PEO into starch-PHBV blends had little or no effect on the rate of weight loss. Starch in blends degraded faster than PHBV and it accelerated PHBV degradation. Also, PHBV did not retard starch degradation. After 125 days of exposure to compost, neat PHBV lost 7% of its weight (0.056% weight loss/day), while the PHBV component of a 50% starch blend lost 41% of its weight (0.328% weight loss/day). PHB and PHV moieties within the copolymer degraded at similar rates, regardless of the presence of starch, as determined by ¹H-NMR spectroscopy. GPC analyses revealed that, while the number average molecular weight (Mn) of PHBV in all exposed samples decreased, there was no significant difference in this decrease between neat PHBV as opposed to PHBV blended with starch. SEM showed homogeneously distributed starch granules embedded in a PHBV matrix, typical of a filler material. Starch granules were rapidly depleted during exposure to compost, increasing the surface area of the PHBV matrix.     

Biodegradation of Coproducts from Industrially Processed Corn in a Compost Environment

Information pertaining to biodegradability of renewable polymeric material is critical for the design and development of single-use biodegradable consumer products. The rate and extent of biodegradation of corn fiber, corn zein, cornstarch, distillers grain, and corn gluten meal were evaluated in compost environments under variable temperature, pH, and moisture conditions. Generally, composts with higher temperature (40°C), neutral pH (7.0), and 50%–60% moisture appeared to be ideal for corn coproduct biodegradation, particularly for corn gluten meal and corn zein. Low moisture conditions slowed biodegradation considerably, but degradation rates improved when moisture content increased up to 60%. Thereafter, increased moisture particularly slowed the degradation of corn gluten meal and corn zein, whereas cornstarch degradation remained unaffected. At low pH (4.0) and high pH (11.0) the rate of degradation of most coproducts was slowed somewhat. Cornstarch degradation was slower at pH 7.0, but degradation improved with increased temperatures. Increase in compost temperature from 25 to 40°C (in 5°C increments) also improved biodegradation of corn fiber and distillers grain. Addition of 1% urea to compost as a nitrogen source decreased the extent of biodegradation nearly 40% for corn gluten meal and corn zein, and 20% for cornstarch samples. Treatment of compost with 0.02% azide inhibited biodegradation of all coproducts, suggesting that the presence of metabolically active microbial cells is required for effective degradation of biobased materials in a compost environment.     

Pilot scale field test for compostable packaging materials in the City of Kassel, Germany

Biodegradable (compostable) packaging materials made from biopolymers (BP) are introduced into the market to reduce the amounts of conventional packaging materials and at the same time be recovered by the municipal organic waste collection system. The processing of this organic waste mixed with biopolymers has been tested in a commercial treatment facility. The safe use of the compost produced from these materials was demonstrated in a full-scale agricultural application test.     

Performance of compostable baby used diapers in the composting process with the organic fraction of municipal solid waste

In modern societies, disposable diapers constitute a significant percentage of municipal solid wastes. They have been traditionally landfilled or incinerated as only limited recycling processes are being implemented in some parts of Europe. With the implementation of separated collection systems for the organic fraction of municipal solid wastes (OFMSWs) and the need to preserve the environment, compostable diapers have appeared in the market to avoid the main environmental impacts associated to non-biodegradable disposable diapers. In this study, a full-scale composting of door-to-door collected OFMSW with a 3% (w/w) of compostable diapers has also been carried out. Previously, lab-scale experiments confirmed that almost 50% of carbon of compostable diapers is emitted as CO₂ under aerobic controlled conditions. The results obtained at full-scale demonstrate that both the composting process and the final end product (compost) are not altered by the presence of compostable diapers in crucial aspects such as pathogenic content, stability and elemental composition (including nutrients and heavy metals). The main conclusion of this study is that the collection of the OFMSW with compostable diapers can be a new way to transform this waste into high-quality compost.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Fiber from DDGS and Corn Grain as Alternative Fillers in Polymer Composites with High Density Polyethylene from Bio-based and Petroleum Sources

The steady increase in production of corn based ethanol fuel has dramatically increased the supply of its major co-product known as distiller’s dried grain with solubles (DDGS). Large amount of DDGS and corn flour are used as an animal feed. The elusieve process can separate DDGS or corn flour into two fractions: DDGS fraction with enhanced protein and oil content or corn flour fraction with high starch content, and hull fiber. This study investigated the feasibility of using fiber from DDGS and corn grain as alternative fillers to wood fiber in high density polyethylene (HDPE) composites made with two different sources of polymers. Two fiber loading rates of 30 and 50% were evaluated for fiber from DDGS, corn, and oak wood (control) to assess changes in various physical and mechanical properties of the composite materials. Two HDPE polymers, a bio-based HDPE made from sugarcane (Braskem), and a petroleum based HDPE (Marlex) were also compared as substrates. The biobased polymer composites with DDGS and corn fibers showed significantly lower water absorption than the Marlex composite samples. The Braskem composite with 30% DDGS fiber loading showed the highest impact resistance (80 J/m) among all the samples. The flexural properties showed no significant difference between the two HDPE composites.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Biodegradability and compostability of polymers—test methods and criteria for evaluation

The treatment of solid waste in controlled composting facilities is an important possibility for reducing garbage. Natural and synthetic polymeric materials can be used for many purposes, for example, as packaging materials, where compostability is required. A prerequisite for official regulations and the decision as to which materials may be composted is investigations on their biodegradability and the quality of the compost produced. Several standardization groups at the ISO, CEN, and DIN are developing definitions, test methods, and classification systems for differentiating compostable from noncompostable materials. The concept which will be standardized and used in Germany is described in detail. It includes characterization of the test material, determination of the biodegradability using laboratory tests such as simple aquatic batch tests and a controlled aerobic composting test, investigation of the disintegration of the test material in industrial or bench-scale composting facilities, and finally, chemical and ecotoxicological analysis of the compost produced.     

Laboratory determination of compost physical parameters for modeling of airflow characteristics

Physical parameters of 12 co-compost cover materials were experimentally determined and predicted variations in airflow characteristics were evaluated under varying moisture contents. Predicted air-filled porosity showed high correlation with measured air-filled porosity, facilitating development of a reliable model of air-filled porosity that makes it possible to predict the effect of varying moisture content and compost bed height on air-filled porosity and permeability. Predicted air-filled porosity decreased with increasing moisture content and compost depth for all materials. Air-filled porosity of corn stalks, oat straw, soybean straw, leaves, alfalfa hay, wheat straw, silage, wood shavings and sawdust was in the range of 38-99%. Turkey litter, soil compost blend and beef manure showed air-filled porosity values less than 30% near saturation and the bottom of pile. In concert with the findings of other researchers, effective particle size of all materials increased with increasing moisture content from 20% to 80% of water holding capacity (WHC). It increased dramatically near saturation. In general, permeability increased with increasing air-filled porosity and decreasing bulk density, but the relationship between permeability and moisture content is complex. Permeability is dependent on the balance between particle size and air-filled porosity. If the influence of aggregated particle size on the permeability is significant, it will compensate for the effect of reduced air-filled porosity caused by compaction and moisture content. In this case, permeability will increase; in the reverse case, it will decrease. Permeability decreased for corn stalks, oat straw, silage, wood shavings, soybean straw, sawdust, turkey litter and wheat straw with increasing moisture content from 20% WHC to 50% WHC, regardless of the depth of the compost bed. But the permeability increased with increasing moisture level from 50% to 80% WHC at moderate to shallow simulated bed depths. The soil compost blend and leaves showed the permeability increasing when the moisture increased not only from 50% to 80% WHC but also from 20% to 50% WHC. Permeability of alfalfa hay and beef manure always decreased with increasing moisture levels and pile depth. In this study the maximum wet bulk density and mechanical strength decreased with increasing the moisture content. The method described for determining physical properties under varying moisture contents and compost bed depths will be very useful for designing and modeling airflow characteristics of a mortality composting process with a variety of materials.     

Degradation of Commercial Biodegradable Packages under Real Composting and Ambient Exposure Conditions

The use of long-lasting polymers as packaging materials for short lived applications is not entirely justified. Plastic packaging materials are often soiled due to foodstuffs and other biological substances, making physical recycling of these materials impractical and normally unwanted. Hence, there is an increasing demand for biodegradable packaging materials which could be easily renewable. Use of biopolymer based packaging materials allows consideration of eliminating issues such as landfilling, sorting and reprocessing through taking advantage of their unique functionality, that is compostability. Composting allows disposal of biodegradable packages and is not as energy intensive compared to sorting and reprocessing for recycling, although it requires more energy than landfilling. The aim of this work was to study the degradation of three commercially available biodegradable packages made of poly (ld-lactide) (PLA) under real compost conditions and under ambient exposure by visual inspection, gel permeation chromatography, differential scanning calorimetry, and thermal gravimetric analysis. A novel technique to study the degradability of these packages and to track the degradation rate under real compost conditions was used. The packages were subjected to composting for 30 days, and the degradation of the physical properties was measured at 1, 2, 4, 6, 9, 15 and 30 days. PLA packages made of 96% l-lactide exhibited lower degradation than PLA packages made of 94% l-lactide, mainly due to their highly ordered structure, therefore, higher crystallinity. The degradation rate changed as the initial crystallinity and the l-lactide content of the packages varied. Temperature, relative humidity, and pH of the compost pile played an important role in the total degradation of the packages. A first order degradation of the molecular weight as a function of time was observed for the three packages.     

Effects of Starch Moisture on Properties of Wheat Starch/Poly(Lactic Acid) Blend Containing Methylenediphenyl Diisocyanate

Methylenediphenyl diisocyanate was found to improve the interfacial interaction between poly(lactic acid)(PLA) and granular starch. The objective of this research was to study the effect of starch moisture content on the interfacial interaction of an equal-weight blend of wheat starch and PLA containing 0.5% methylenediphenyl diisocyanate by weight. Starch moisture (10% to 20%) had a negative effect on the interfacial binding between starch and PLA. The tensile strength and elongation of the blend both decreased as starch moisture content increased. At 20% moisture level, the starch granules embedded in the PLA matrix were observed to be swollen, resulting in poor strength properties and high water absorption by the blend.     

Effect of the composting substrate on biodegradation of solid materials under controlled composting conditions

Biodegradability under composting conditions is assessed by test methods, such as ASTM D 5338-92, based on the measurement of CO₂ released by test materials when mixed with mature compost and maintained in a controlled composting environment. However, in real composting, biodegradation occurs in fresh waste. To clarify this point, the biodegradation of paper and of a starch-based biodegradable thermoplastic material, Mater-Bi ZI01U, was followed by measuring the weight loss of samples introduced either into a mature compost or into a synthetic waste. The weight loss in mature compost was higher at the beginning but tended to decrease; in synthetic waste a first lag phase was followed by an exponential phase. Complete degradation of paper was noticed simultaneously in the two substrates (after 25 days). The bulkier Mater-Bi samples were fully degraded after 20 days in fresh waste, but after 45 days in mature compost. Therefore, the test methods using mature compost as a substrate can possibly underestimate the biodegradation rate occurring in fresh waste, i.e., in real composting plants, and have to be considered as conservative test methods. The test procedure described in this paper seems very suitable as a screening method to verify the compostability of plastic materials in a composting environment.     

Grafting of Glycidyl Methacrylate onto Poly(lactide) and Properties of PLA/Starch Blends Compatibilized by the Grafted Copolymer

Poly(lactide)-graft-glycidyl methacrylate (PLA-g-GMA) copolymer was prepared by grafting GMA onto PLA in a batch mixer using benzoyl peroxide as an initiator. The graft content was determined with the ¹H-NMR spectroscopy by calculating the relative area of the characteristic peaks of PLA and GMA. The result shows that the graft content increases from 1.8 to 11.0 wt% as the GMA concentration in the feed varies from 5 to 20 wt%. The PLA/starch blends were prepared by the PLA-g-GMA copolymer as a compatibilizer, and the structure and properties of PLA/starch blends with or without the PLA-g-GMA copolymer were characterized by SEM, DSC, tensile test and medium resistance test. The result shows that the PLA/starch blends without the PLA-g-GMA copolymer show a poor interfacial adhesion and the starch granules are clearly observed, nevertheless the starch granules are better dispersed and covered by PLA when the PLA-g-GMA copolymer as a compatibilizer. The mechanical properties of the PLA/starch blends with the PLA-g-GMA copolymer are obviously improved, such as tensile strength at break increasing from 18.6 ± 3.8 MPa to 29.3 ± 5.8 MPa, tensile modulus from 510 ± 62 MPa to 901 ± 62 MPa and elongation at break from 1.8 ± 0.4 % to 3.4 ± 0.6 %, respectively, for without the PLA-g-GMA copolymer. In addition, the medium resistance of PLA/starch blends with the PLA-g-GMA copolymer was much better than PLA/starch blends.     

Enhanced degradable yard waste collection bag behavior in a field-scale composting environment

The degradation of four formulations of yard waste-filled collection bags was evaluated in a field-scale test of 15.5- or 31-m-long windrows at a community yard waste composting site. Variables of bag contents, bag chemical composition, and length of exposure were evaluated. Chemical compositions of the bags included (1) low-density polyethylene (LDPE) + 6% cornstarch + 2 levels of prooxidant, (2) LDPE + 9% cornstarch + prooxidants, and (3) LDPE without cornstarch but with photooxidation enhancers. Results showed that all products weakened and/or disintegrated to some extent. However, the bags with 6% starch disintegrated too slowly to allow timely processing of the compost. The bags with 9% starch and other additives to promote multiple degradation mechanisms degraded at the fastest rate of those evaluated here. The photodegradable bags with solar exposure during composting disintegrated rapidly, but when turned to expose new surfaces to light, further strength losses occurred slowly.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.     

Effects of biodegradable plastic components on metabolism of an estuarine benthos

We examined the metabolic response of an estuarine benthic community to additions of three materials being considered for use in manufacture of biodegradable substitutes for plastics. Diver-collected cores containing benthos were dosed with 59 g/m² of three test materials, cornstarch, a bacterial polyester (PHBV), and ethylene vinyl alcohol (EVOH), or left undisturbed as controls. Fluxes of dissolved nutrients (ammonia, nitrate + nitrite, phosphate, silica) and dissolved inorganic carbon (DIC) were similar in control cores and cores dosed with EVOH during a 1-month test period at 20°C. Fluxes in cores dosed with starch and PHBV differed significantly from controls but not from each other. After 2 weeks of incubation, production of DIC was higher in cores containing starch and PHBV, while efflux of ammonia, nitrate, and nitrite was reduced. After 4 weeks of incubation, production of DIC was similar among all treatments and controls, while efflux of ammonia was high in the starch- and PHBV-containing cores compared to controls and cores with EVOH. Fluxes of silica and phosphate were similar in all cores during the experiment. These results indicate that both starch and PHBV are carbon-rich substrates readily metabolized by the benthic community but that their presence significantly alters normal nutrient exchange patterns. This response is expected because of the high carbon-to-nitrogen ratio of starch and PHBV and indicates that impacts of these two materials would be similar. However, the high biological oxygen demand of such materials and resulting disturbance of normal nutrient regeneration patterns of the benthos (delayed ammonia efflux and potential stimulation of denitrification) must be considered in developing strategies for their disposal.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.     

Photodegradation and Biodegradation Study of a Starch and Poly(Lactic Acid) Coextruded Material

To simulate the behavior of agricultural mulch coextruded poly(lactic acid)(PLA)/starch films, two stages were carried out. The first was an ultraviolet treatment (UV) at 315 nm, during which glass transition temperature T_g, weight, and molecular weight (MW) decreased and a separation between PLA and starch phase was observed. For the second stage, the mineralization of the carbon of the material was followed using the ASTM (D 5209–92 and 5338–92) and ISO/CEN (14852 and 14855) standard procedures. To measure the biodegradability of polymer material, the assessment of the carbon balance allowed determination of the distribution between the carbon rate used to the biomass synthesis or the respiration process (released CO₂), as well as the dissolved organic carbon into the culture medium and the carbon in the residual insoluble material. The influence of the nature of the medium and the standardized procedures on the final rate of biodegradation was investigated. Whatever the standardized method, the biodegradation percentage was significantly stronger in liquid medium (92.4–93.4) than on inert medium (80–83%). In the case of the compost process, only released CO₂ was measured and corresponded to 79.1–80.3%.     

Temperature Effects on Soil Mineralization of Polylactic Acid Plastic in Laboratory Respirometers

A respirometric system was used to analyze the biodegradation of high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films in soil under laboratory conditions. The respirometric system consisted of air-conditioning pretraps, a soil reactor, and a carbon dioxide (CO₂) posttrap. A 200-g homogeneous soil mixture of all-purpose potting soil : manure soil : sand [1 : 1 : 1 (w/w)] and 1.5 g of PLA plastic films in 1 × 1-cm² squares was added to each bottle. The respirometers were placed in a 28, 40, or 55°C water bath for 182 days. Treatments (three replicates) included native corn starch (positive control), polyethylene (Glad Cling Wrap; negative control), and three PLA films: Ca-I (Cargill Dow Polymers LLC, monolayer), GII (Cargill Dow Polymers LLC, Generation II), and Ch-I (Chronopol; monolayer). The degree of polymer mineralization was indicated by the cumulative CO₂ liberated from each respirometer. The initial average mineralization rate and total percentage mineralized of the PLA plastic films at 28, 40, and 55°C was 24.3, 41.5, and 76.9 mg/day with a 27, 45, and 70% carbon loss, respectively. No decrease in soil pH was observed after 182 days of mineralization. Hence, increase in soil temperature drastically enhanced the biodegradation of PLA plastic films in soil under laboratory conditions (P < 0.0001).     

Enhanced Interfacial Adhesion and Characterisation of Recycled Natural Fibre-Filled Biodegradable Green Composites

The structural, thermal, mechanical, and biodegradable properties of composite materials made from polylactide (PLA) and agricultural residues (arrowroot (Maranta arundinacea) fibre, AF) were evaluated. Melt blended glycidyl methacrylate-grafted polylactide (PLA-g-GMA) and coupling agent-treated arrowroot fibre (TAF) formed the PLA-g-GMA/TAF composite, which had better properties than the PLA/AF composite. The water resistance of the PLA-g-GMA/TAF composite was greater than that of the PLA/AF composite; the release of PLA in water from the PLA/AF and PLA-g-GMA/TAF composites indicated good biological activity. The PLA-g-GMA/TAF material had better mechanical properties than PLA/AF. This behaviour was attributed to better compatibility between the grafted polymer and TAF. The results indicated that the T_g of PLA was increased by the addition of fibre, which may have improved the heat resistance of PLA. Furthermore, the mass losses following burial in soil compost indicated that both materials were biodegradable, especially at high levels of AF or TAF substitution.