Hydroxyl radical dominated ibuprofen degradation by UV/percarbonate process: Response surface methodology optimization, toxicity, and cost evaluation.

Ibuprofen (IBP) is a typical nonsteroidal anti-inflammatory drug with a wide range of applications, large dosages, and environmental durability. Therefore, ultraviolet-activated sodium percarbonate (UV/SPC) technology was developed for IBP degradation. The results showed that IBP could be efficiently removed using UV/SPC. The IBP degradation was enhanced with prolonged UV irradiation time, with the decreasing IBP concentration and the increasing SPC dosage. The UV/SPC degradation of IBP was highly adaptable to pH ranging from 4.05 to 8.03. The degradation rate of IBP reached 100% within 30 min. The optimal experimental conditions for IBP degradation were further optimized using response surface methodology. IBP degradation rate reached 97.3% under the optimal experimental conditions: 5 µM of IBP, 40 µM of SPC, 7.60 pH, and UV irradiation for 20 min. Humic acid, fulvic acid, inorganic anions, and natural water matrix inhibited the IBP degradation to varying degrees. Scavenging experiments of reactive oxygen species indicated that hydroxyl radical played a major role in the UV/SPC degradation of IBP, while carbonate radical played a minor role. Six IBP degradation intermediates were detected, and hydroxylation and decarboxylation were proposed as the primary degradation pathways. An acute toxicity test, based on the inhibition of luminescence in Vibrio fischeri, indicated that the toxicity of IBP during UV/SPC degradation decreased by 11%. An electrical energy per order value of 3.57 kWh m-3 indicated that the UV/SPC process was cost-effective in IBP decomposition. These results provide new insights into the degradation performance and mechanisms of the UV/SPC process, which can potentially be used for practical water treatment in the future.

Polypropylene microplastics aging under natural conditions in winter and summer and its effects on the sorption and desorption of nonylphenol.

Plastics in the environment undergo various aging effects. Due to the changes in physical and chemical properties, the sorption behavior of aged microplastics (MPs) for pollutants differs from that of pristine MPs. In this paper, the most common disposable polypropylene (PP) rice box was used as the source of MPs to study the sorption and desorption behavior of nonylphenol (NP) on pristine and naturally aged PPs in summer and winter. The results show that summer-aged PP has more obvious property changes than winter-aged PP. The equilibrium sorption amount of NP on PP is summer-aged PP (477.08 µg/g) > winter-aged PP (407.14 µg/g) > pristine PP (389.29 µg/g). The sorption mechanism includes the partition effect, van der Waals forces, hydrogen bonds and hydrophobic interaction, among which chemical sorption (hydrogen bonding) dominates the sorption; moreover, partition also plays an important role in this process. Aged MPs' more robust sorption capacity is attributed to the larger specific surface area, stronger polarity and more oxygen-containing functional groups on the surface that are conducive to forming hydrogen bonds with NP. Desorption of NP in the simulated intestinal fluid is significant owning to intestinal micelles' presence: summer-aged PP (300.52 µg/g) > winter-aged PP (291.08 µg/g) > pristine PP (287.12 µg/g). Hence, aged PP presents a more vital ecological risk.

Adsorption of acetone, ethyl acetate and toluene by beta zeolite/diatomite composites: preparation, characterization and adsorbability.

The hierarchical porous composites (Beta/Dt) were prepared by secondary growth method using natural diatomite and beta zeolite. Moreover, XRD, SEM, and BET characterize the composite's composition, surface structure, and pore structure. The adsorbability of Beta/Dt was evaluated by adsorption of three common volatile organic compounds (VOCs) of the printing industry: acetone, ethyl acetate, and toluene. The results show that under the optimum preparation condition, the adsorption capacities of the three VOCs on Beta/Dt were about 3.5 times those of pure beta zeolite and 4.7-35.3 times those of diatomite, respectively. It indicates the synergistic adsorption effect between beta zeolite and diatomite. The superior adsorption capacity of Beta/Dt can be attributed to the suitable micropore size, the increase of the diffusion channels, and the chemical adsorption on modification diatomite. The adsorption of acetone, ethyl acetate, and toluene on Beta/Dt conformed to the pseudo-second-order kinetic model. In contrast, adsorption isotherms conformed to the Langmuir model, meaning that both physical and chemical adsorption occurred simultaneously during the adsorption process, and the adsorption belonged to the monolayer adsorption. The chemical adsorption mechanism can be ascribed to the nucleophilic reaction between the three VOCs (acetone, ethyl acetate, and toluene) and Beta/Dt with positive charges resulting from the modification diatomite. Furthermore, the composite could still keep more than 90% of the adsorption capacity of the original adsorbent after five regeneration cycles.

Enhanced degradation mechanism of tetracycline by MnO2 with the presence of organic acids.

In this study, we constructed MnO2/organic acid (OA) systems using MnO2 colloid, the most reactive phase of Mn(IV), and two kinds of OA (oxalic acid and l-tartaric acid). We investigated the effect of OA on tetracycline (TC) degradation by MnO2. The results show that both OA obviously accelerate TC degradation by MnO2. Mn(III) formed during the reaction lead to the acceleration. Mn(III)-oxalate complex formed in oxalic acid system resulted in the lower degradation efficiency than that in l-tartaric acid system. The acceleration of oxalic acid was decreased when the concentration was more than 75 µM, and even completely disappeared with the concentration of 500 µM, owning to the fact that excess oxalic acid decreased the pH and some MnO2 was fast reduced to Mn2+ by oxalic acid and unable to react with TC. The impact of pH on TC degradation resulted from the influences of H+ on MnO2 redox potentials and TC deprotonation. And acidic conditions accelerated TC degradation. The addition of Mg2+, Ca2+, Fe3+ and Zn2+ exhibited an inhibitory effect in both systems for their occupying reactive sites on MnO2 surface and blocking the access of TC to MnO2. Similar intermediates in the two systems were detected, indicating a similar TC degradation mechanism including a series of reactions like dehydration, hydroxylation and oxidation. The MnO2/OA system provides an efficient treatment of TC in wastewater. And it is also noticeable that MnO2/OA system should also have an important effect on the fate of pollutants in environment, from our results.

Photochemical degradation of ß-hexachlorocyclohexane in snow and ice.

Hexachlorocyclohexane (HCH), a typical organochloride pesticide, is one of the persistent organic pollutants. Despite the ban on technical grade HCH, it has been continuously observed at a steady level in the environment. The photochemical degradation of ß-HCH in snow and ice under ultraviolet (UV) irradiation was investigated in this study. The effects of pH as well as common chemical components in snow on the degradation kinetics were investigated. In addition, the photodegradation products were determined and the reaction mechanism was hypothesized. The results showed that under UV irradiation, ß-HCH can be photolyzed in snow and ice, with the photochemical degradation process conforming to the first-order kinetic equation. Changing the pH and adding Fe2+ had minimal effect on the photochemical degradation kinetics, while the presence of acetone, NO2-, NO3- and Fe3+ significantly inhibited the process. The addition of hydrogen peroxide slightly inhibited the photochemical degradation of ß-HCH. Finally, the reaction rate, products and degradation mechanism of ß-HCH in snow were compared with those in the ice phase. The photochemical degradation rate of ß-HCH in snow was approximately 24 times faster than that in the ice phase. The photolysis product of ß-HCH in snow was α-HCH, produced by the isomerization of ß-HCH. However, in ice, in addition to α-HCH, pentachlorocyclohexene was produced by dechlorination. The results of this study are helpful in understanding the transformation of organochlorine pesticides in snow and ice, as well as in providing a theoretical basis for snow and ice pollution prevention and control.

Ag NPs decorated C-TiO2/Cd0.5Zn0.5S Z-scheme heterojunction for simultaneous RhB degradation and Cr(VI) reduction.

In this study, heterojunction photocatalysts, XAg@C-TCZ, based on MOF-derived C-TiO2 and Cd0.5Zn0.5S decorated with Ag nanoparticles (Ag NPs) were successfully synthesized through hydrothermal and calcination methods. The catalytic effectiveness of XAg@C-TCZ was evaluated by simultaneous photocatalytic degradation of rhodamine B (RhB) and reduction of Cr(VI) under simulated sunlight irradiation. The presence of the Z-scheme heterojunction was demonstrated through trapping experiments, X-ray photoelectron spectroscopy (XPS), time-resolved photoluminescence (PL) investigations, and electron spin resonance (ESR) spectroscopy. With an initial RhB and Cr(VI) concentration of 7 mg L-1 and 5 mg L-1, the catalyst 10Ag@C-TCZ achieved a simultaneous removal of 95.2% and 95.5% within 120 min, respectively. With the same catalyst, the degradation rate of RhB was 2.75 times higher and the reduction rate of Cr(VI) was 9.3 times higher compared to pure Cd0.5Zn0.5S. Total organic carbon (TOC) analysis confirmed the extent of mineralization of RhB, while the reduction of Cr(VI) was corroborated by XPS. Compared to pure RhB and Cr(VI) solutions, the reaction rates are smaller in the solution containing both contaminants, which is attributed to the competition for ·O2-. 10Ag@C-TCZ also exhibited a stable catalytic performance in tap water and lake water. This work provides a new perspective on the construction of heterojunctions with doped MOF derivatives for the purification of complex pollutant systems.

Photodegradation of dissolved organic matter of chicken manure: Property changes and effects on Zn2+/Cu2+ binding property.

Untreated livestock manure contains high concentrations of dissolved organic matter (DOM), which can enter the environment through leaching and eluviation, showing an important impact on the environment. In this research, fresh chicken manure from a large-scale chicken farm was collected as the source of DOM. The infrared spectrum of the original DOM was characterized. TOC analysis, UV spectrum and 3D fluorescence spectrum were used to measure the properties of DOM before and after photodegradation. Infrared spectroscopy results show that chicken manure DOM may contain aliphatic and aromatic compounds, alcohols, phenols, polysaccharides and some protein substances; In three systems, the order of TOC removal rates of DOM was water + UV system (85%) > > water + simulated sunlight system (7.2%) > ice + simulated sunlight system (4.5%); Changes of UV spectra, fluorescence spectra, molecular weight distribution and pH value show that, in three systems, as the illumination time increased, photodegradation reduced pH value of the systems, aromaticity and humus contents of DOM, while increased the proportion of medium and/or small molecular weight components of DOM. The amounts of all these changes were proportional to DOM photodegradation rates in the system. The binding ability of DOM with Cu2+ and Zn2+ in water solution decreased significantly after the photodegradation.

Removal of tetracyclines from aqueous solutions by electrocoagulation/pecan nutshell coupling processes: synergistic effect and mechanism.

The present work compared electrocoagulation (EC)/pecan shell (PS) coupling process with a simple electrocoagulation (EC) process for the removal of tetracyclines (TCs). The results indicated that the addition of appropriate PS could lead to the enhancement of the removal efficiency and decrease of operating time via synergistic influence, including conventional EC process, biomass materials adsorption, charge neutralization and coordination adsorption. The ideal condition for the coupling process was 2.5 mA/cm2 for current density and 3 cm for plate spacing. Based on the optimum condition, when the dosage of PS was 5 g/L, the initial concentration of tetracycline hydrochloride (TC), oxytetracycline hydrochloride (OTC) and chlortetracycline hydrochloride (CTC) was 250 mg/L, the removal rate of PS was 55.90%, 45.10% and 14.98% higher than those of EC process after 40 min treatment. In addition, compared to conventional EC process, the unit energy demand (UED) decreased by 49.62%, 53.2 4% and 26.35% and the unit electrode material demand (UEMD) decreased by 49.80%, 85.65% and 44.37%, respectively, which means more energy conservation and environmental protection.

Fabrication of a magnetic ternary ZnFe2O4/TiO2/RGO Z-scheme system with efficient photocatalytic activity and easy recyclability.

A magnetic composite based on TiO2 nanosheets, ZnFe2O4 and reduced graphene oxide (RGO) was synthesized by a one-step hydrothermal synthesis method, which possessed the band structure of a Z-scheme photocatalytic system. The properties and structures of the samples were characterized by XRD, UV-Vis DRS, Raman spectroscopy, SEM, EDS, XPS and PL spectroscopy. Compared with TiO2 nanosheets and the TiO2/RGO composite, the obtained ternary composite with 3 wt% RGO exhibited a significant enhancement in photocatalytic activities, attributed to the efficient charge separation induced by the fabricated Z-scheme system. About 99.7% of p-nitrophenol (p-NP) degraded within 60 min under simulated solar irradiation. Trapping experiments showed that superoxide anions (˙O2 -) and hydroxyl radicals (˙OH) were the main active species in the p-NP photocatalytic degradation. Finally, a possible photocatalytic mechanism of Z-scheme ZnFe2O4/TiO2/RGO was proposed based on the results of trapping experiments and the energy bands of TiO2 and ZnFe2O4.

Effects of oxalic acid on Cr(VI) reduction by phenols in ice.

Since Cr(VI) is highly toxic, the environmental reduction of Cr(VI) to Cr(III) has attracted significant attention. Oxalic acid, a primary component of dissolved organic matter (DOM), is widely distributed throughout the natural environment but the reduction of Cr(VI) by oxalic acid is insignificant at the low concentrations present in the environment; however, the reduction of Cr(VI) is accelerated significantly in ice. In terms of combined pollution, Cr(VI) can coexist with other organic pollutants in the environment but the impact of organic pollutants on the reduction of Cr(VI), changes to the organic pollutants themselves, and the role of oxalic acid in these reactions are unknown. In this study, we investigated redox reactions between Cr(VI) and phenolic compounds in ice (- 15 °C) in the presence of oxalic acid and compared these to room temperature redox reactions in aqueous solutions (20 °C). While these redox reactions were negligible in aqueous solution, they were significantly accelerated in ice under acidic conditions, which was primarily attributed to the freeze concentration effect. Oxalic acid has two functions in these redox reactions; the first is to provide the H+ required for the reaction and the second is to serve as a reducing agent. When oxalic acid and phenolic pollutants coexist, Cr(VI) preferentially reacts with the phenolic compounds. Phenol, 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP) were each demonstrated to reduce Cr(VI) in ice, but the reaction rate and overall reactivity of these three phenolic compounds are different.

Comparison of the photoconversion of 1-chloronaphthalene and 2,3-dichlornaphthalene in water.

In this work, the photoconversion of 1-chloronaphthalene (CN-1) and 2,3-dichlornaphthalene (CN-10) under the simulated sunlight had been studied. The results showed that the photoconversion of CN-1 and CN-10 obeyed the first-order kinetics model. NO2 -, NO3 -, Fe3+ and Fe2+ extensively present in natural water can accelerate CN-1 photoconversion via generating ·OH, which may induce indirect photooxidation of CN-1. The photoproducts were treated by the derivatization method and analyzed by GC-MS after being irradiated for 6 h. Ten products were characterized for CN-1 and CN-10, and there were six common products. On this basis, the photoconversion pathways of CN-10 and CN-1 were proposed, and both of them have a similar conversion mechanism.

Hydrothermal in situ synthesis of Rb and S co-doped Ti-based TiO2 sheet with a thin film showing high photocatalytic activities.

TiO2 is considered as one of the most promising semiconductor photocatalysts used to degrade organic pollutants. Element doping has a good effect on improving the properties of TiO2. Herein, by using Rb2SO4, we explored the in situ synthesis of Ti-based TiO2 sheets with a thin film through a hydrothermal reaction. Then, the photocatalyst was successfully fabricated by calcination. All samples were characterized by FT-IR, XRD, SEM, XPS, PL and UV-vis DRS measurements. The results indicate that the S doping together with surface hydroxyl groups lead to the band gap narrowing. S and a trace amount of Rb element can enable the formation of uniform microspheres on the surface of the Ti plate and the major phase transformed from titanium to anatase. The band gap absorption extended from 400 nm to 600 nm. The photocatalytic properties were investigated by performing the degradation of methyl orange (MO) and 4-chlorophenol (4-CP) in the aqueous solutions under UV and simulated sunlight. In the series of TiO2 photocatalysts, Rb/S/TiO2-48 shows the best photocatalytic efficiency and good photocatalytic performance on recycling. Interestingly, when H2O2 was added to the MO aqueous solution, a synergistic effect of the TiO2 thin film and H2O2 on degrading the pollutant was observed.

Photoconversion of 2-Chloronaphthalene in Water.

The photoconversion of 2-chloronaphthalene (CN-2) in water in a simulated sunlight system was investigated. The photoconversion efficiency, photoproducts and mechanisms were inspected, and the effects of inorganic ions (NO3-, NO2-) and fulvic acid (FA) were discussed. The results showed that CN-2 could be transformed in water under the irradiation. NO3- and NO2- promoted the photoconversion of CN-2 owing to ·OH generated by the photolysis of NO3- and NO2-; FA at a lower concentration promoted the photoconversion, but it had an inhibition effect at a higher concentration. It was demonstrated that the acidic conditions promoted the photoconversion of CN-2 by the active groups such as superoxide radical anion, hydrogen peroxide and hydroxyl radical produced in the system. Eight photoproducts of CN-2 were characterized by the GC-MS method and the possible photoconversion mechanisms were proposed accordingly.

The photoconversion of gamma-hexachlorocyclohexane under UV irradiation in water, snow and ice.

The photochemistry of organic pollutants has received increasing attention in ice and snow. In this work, the photoconversion of gamma-hexachlorocyclohexane (γ-HCH) under UV irradiation was investigated in water, snow and ice. The photoconversion rate, products and mechanisms were inspected, and the effect of inorganic ions (NO2(-), NO3(-), HCO3(-) and Fe(2+)) was discussed. The results showed that γ-HCH could be photoconverted in water, snow and ice, with the photoconversion rate being fastest in snow, and slowest in ice. All photoconversion could be described by the first-order kinetics model. In water, snow and ice, the common photoproducts of γ-HCH were alpha-hexachlorocyclohexane (α-HCH) and pentachlorocyclohexene. α-HCH was generated by a change in the bonding of a chlorine atom in γ-HCH; pentachlorocyclohexene was generated by the removal of a molecule of chlorine hydride from a molecule of γ-HCH. Different concentrations of NO2(-), NO3(-) and HCO3(-) all inhibited the photoconversion of γ-HCH, and the inhibition effect decreased with increasing concentrations of NO2(-) and NO3(-), but increased with the increasing concentrations of HCO3(-). Different concentrations of Fe(2+) promoted the photoconversion of γ-HCH in water and ice, but had little effect in snow.

Photo-Fenton effect of 4-chlorophenol in ice.

The photoconversion of 4-chlorophenol (4-CP) in a simulated sunlight-Fenton system was investigated in ice and aqueous solution. It was found that the hydroxyl radical (OH) had an important effect on the photoconversion of 4-CP in both phases, but the effects of Cl(-), SO4(2-), NO3(-), and HCO3(-) were different. In aqueous solution, the photoconversion efficiency of 4-CP was proportional to the OH concentration, and hence, Cl(-) and HCO3(-) as OH scavengers prohibited the photoconversion; SO4(2-) had little effect; NO3(-) promoted the process under certain conditions owing to OH being generated by the photolysis of NO3(-). In ice, however, the photoconversion efficiency of 4-CP was not proportional to the concentration of OH. The photoconversion efficiency of 4-CP increased with increasing concentrations of all ions, although the OH remained almost constant, only increasing or decreasing slightly. This provides new evidence for the presence of a quasi-liquid layer (QLL). Hydroxylation products were detected in both phases. All photoproducts in aqueous solution contained only a single benzene ring, whereas in ice, dimers were also detected.

Comparison of the photoconversion of para-chlorophenol under simulated sunlight and UV irradiation in ice.

The photochemistry of para-chlorophenol (4-CP) was studied under simulated sunlight (lambda > 300 nm) and UV irradiation by using a 125 W high-pressure mercury lamp with or without a hard glass as light source in an ice matrix. The experiments were carried out in a photochemical cold chamber reactor at -14 to -12 degrees C. The photoconversion rate, photoproducts and photoconversion mechanism of 4-CP were all inspected and compared. The results show that the 4-CP photoconversion obeys the first order kinetic model and its photoconversion rate is highly affected by the initial concentration of 4-CP, light intensity and water quality. It is found that the conversion rate of 4-CP under UV irradiation is higher than that under simulated sunlight irradiation. The intermediate products of 4-CP were characterized by GC-MS, HPLC-ESI-MS and HPLC techniques and the possible photoconversion mechanism was proposed accordingly. It is concluded that the mechanism and photoproducts of 4-CP photolysis in ice are different from those in water, and the photoproducts and photoconversion pathways of 4-CP in ice varied with different light sources.

[Study on running efficiency of more spots divisional influent of anaerobic baffled reactor].

The experimentation studied running efficiency of divisional influent mode to anaerobic baffled reactor (ABR) compared with single influent anaerobic baffled reactor that had four compartments. The results showed that the average soluble COD removal rate of single influent was 30%, but divisional influent anaerobic baffled reactor was 35%, and the highest value might reach to 45%, the removal rate of COD was improved over 5% than single influent anaerobic baffled reactor. The main biological processes were micro-aerobic hydrolysis and acidification, at the same time the methane-producing bacteria existed too. The means of divisional influent could avoid high organic loading in the first compartment that led the volatile fatty acids (VFA) to accumulate overly and might improve the fact of lacking organic substance at the back compartment and let reactor to have high microorganism activity and improve ability of reducing contamination.

Kinetics and mechanism of para-chlorophenol photoconversion with the presence of nitrite in ice.

The photochemistry of para-chlorophenol (4-CP) under UV irradiation by using a 125-W high-pressure mercury lamp as light source with the presence of nitrite in a solid water ice matrix had been studied. The experiments were carried out in a photochemical cold chamber reactor at -14 to -12 degrees C. Each influence factor of the 4-CP photoconversion kinetics in the water ice was inspected. The results show that the 4-CP photoconversion obeys the first-order kinetics model and the initial concentration of 4-CP, the initial concentration of nitrite, pH value, light intensity, inorganic ions and the water quality all have significant influence on the photoconversion rate. In addition, nine intermediate products were characterized by GC-MS, HPLC-ESI-MS and HPLC techniques and the possible photoconversion mechanism was proposed accordingly. It is concluded that the mechanism and photoproducts of 4-CP photolysis in ice are changed due to the presence of NO(2)(-).

[Effects of grazing on architecture and small-scale pattern of grasses on artificial grassland in subtropical zone].

This study was conducted on a 5-year artificial grassland in subtropical zone of South China. The main types of established artificial grassland there were Dactylis glomerata-Lolium prenne-Trifolium repens and D. glomerata-T. repens pastures. Four grazing intensities were designed, i.e., CK (no grazing), G1 (6 adult sheep x hm(-2)), G2 (7.5 adult sheep x hm(-2)) and G3 (10 adult sheep x hm(-2)), and all the grazing plots were rotationally grazed. The architecture and small-scale pattern of grasses on the grazed and ungrazed grassland were discussed. After a period of 5-year grazing, the plant basal width and sward height of D. glomerata and T. pratense decreased gradually. In treatments CK, G1, G2 and G3, the basal width of D. glomerata was 6-8, 2-4, 0-2 and 0-2 cm, and that of T. pratense was 1-1.2, 6-8, 4-6 and 2-4 cm, respectively. The tuft density of D. glomerata in treatments CK, G1, G2 and G3 was 60, 95.1, 210.2 and 160 tufts x m(-2), respectively. The tiller number per plant of D. glomerata decreased, while its tuft density increased significantly due to the increased grazing intensity. With the increase of grazing intensity, the internode length of T. repens decreased, while its branching angle increased. The average internode length in treatments CK, G1, G2 and G3 was 2.04, 1.69, 1.64 and 1.51 cm, while the branching angle was 46.5, 65, 73 and 77.3 degrees, respectively. The average leaf density of T. repens in treatments CK, G1, G2 and G3 was 2.9, 13.0, 4.7 and 1.0 x m(-2), while the relevant stolon density was 19.9, 101, 142 and 82.6 m x m(-2), respectively. Under moderate grazing intensity, both the leaf and stolon densities of T. repens increased. The main scale on small pattern of D. glomerata, T. repens and T. pratense was 2 cm x 2 cm, which was further decreased under higher grazing intensity in the treatments of D. glomerata and T. pratense. Considering the heterogeneity of environmental resources, the change of the architecture and small-scale pattern could be regarded as an adaptation of grasses under grazing disturbance.

[Effect of cutting periodicity on energy allocation and architecture of Trifolium repens].

On the subtropical mountain swards, the effect of cutting periodicity on energy allocation, module density, number of branches and branching angle of T. repens were significant, With cutting periodicity raised, the energy allocation of stolon increased steadly, the caloric content of unit stolon dropped gradually, and the changing pattern of leaf density, stem density, branch number and internode's length was from low to high, and then to low. The branching intensity of T. repens ranged from 15 to 23.7 branches.m-2, and branching angle raried from 49.5 degrees to 60.2 degrees while the cutting periodicity differed.