Performance of a biofilter for the removal of high concentrations of styrene under steady and non-steady state conditions

The performance of a laboratory scale perlite biofilter inoculated with a mixed culture was evaluated for gas phase styrene removal under various operating conditions. Experiments were carried out by subjecting the biofilter to different flow rates (0.15–0.9 m³ h⁻¹) and concentrations (0.03–17.3 g m⁻³), corresponding to inlet loading rates varying from as low as 3 g m⁻³ h⁻¹ to as high as 1390 g m⁻³ h⁻¹. A maximum elimination capacity (EC) of 382 g m⁻³ h⁻¹ was achieved at an inlet loading rate of 464 g m⁻³ h⁻¹ with a removal efficiency of 82%. The high elimination capacity reached with this system could have been due to the dominant presence of filamentous fungi among others. The impact of relative humidity (RH) (30%, 60% and >92%) on the biofilter performance was evaluated at two constant loading rates, viz., 80 and 260 g m⁻³ h⁻¹, showing that inhibitory effects were only significant when combining the highest loads with the lowest relative humidities. Biomass distribution, moisture content and concentration profiles along the bed height were significantly dependent on the relative humidity of the inlet air and on the loading rate. The dynamic behaviour of the biofilter through vigorous short and long-term shock loads was tested at different process conditions. The biofilter was found to respond apace to rapid changes in loading conditions. The stability of the biomass within the reactor was apparent from the fast response of the biofilter to recuperate and handle intermittent shutdown and restart operations, either with or without nutrient addition.     

Thermophilic biofiltration of H2S and isolation of a thermophilic and heterotrophic H2S-degrading bacterium, Bacillus sp. TSO3

Thermophilic biofiltration of H₂S-containing gas was studied at 60 °C using polyurethane (PU) cubes and as a packing material and compost as a source of thermophilic microorganisms. The performance of biofilter was enhanced by pH control and addition of yeast extract (YE). With YE supplement and pH control, H₂S removal efficiency remained above 95% up to an inlet concentration of 950 ppmv at a space velocity (SV) of 50 h⁻¹ (residence time = 1.2 min). H₂S removal efficiency strongly correlated with the inverse of H₂S inlet concentrations and gas flow rates. Thermophilic, sulfur-oxidizing bacteria, TSO3, were isolated from the biofilter and identified as Bacillus sp., which had high similarity value (99%) with Bacillus thermoleovorans. The isolate TSO3 was able to degrade H₂S without a lag period at 60 °C in liquid cultures as well as in the biofilter. High H₂S removal efficiencies were sustained with a periodic addition of YE. This study demonstrated that an application of thermophilic microorganism for a treatment of hot gases may be an economically attractive option since expensive pre-cooling of gases to accommodate mesophilic processes is not required.     

Evaluation of gas removal and bacterial community diversity in a biofilter developed to treat composting exhaust gases

The performance of a new, but simply constructed, biofilter system, developed to purify composting exhaust air, was evaluated. The biofilter was packed with mature compost mixed with activated carbon and sludge sourced from a wastewater treatment plant. An alternating air flow system and a bioaerosol reduction device were designed to prevent pressure drop and reduce bioaerosol release. Experimental results demonstrated that satisfactory removal efficiencies of nitrogen-containing compounds, sulfur-containing compounds, fatty acids, total hydrocarbon and odor were achieved at an empty bed retention time (EBRT) of 30s. No significant acidification or alkalinity in the biofilter was observed, and the system was characterized by a small pressure drop and a low level of bioaerosol emission. Denaturing gradient gel electrophoresis (DGGE) and fluorescence in situ hybridization (FISH) techniques were used to uncover the changes in the bacterial community of the biofilter during the deodorization processes. A minimum of 16 bands were observed in the DGGE profile. Phylogenetic analysis revealed the phylum of Proteobacteria to be predominant, followed by Actinobacteria, Bacteroidetes, and Firmicutes, in descending order. However, the occurrence and predominance of specific bacterial species varied with the environmental conditions of the biofilter. Our results demonstrate - from both an engineering and biological point of view - the feasibility of the biofilter system described herein in purifying the gases derived from composting food waste.     

Dynamic tensile behavior of multi phase high yield strength steel

Results of uni-axial tensile testing of multi phase 800 High Yield strength steel (MP800HY) at different strain rates (0.001–750 s⁻¹) are reported here. Flat specimens having gauge length 10 mm, width 4 mm and thickness 2 mm were tested to determine the mechanical properties of MP800HY under tensile loads. The quasi-static tests (0.001 s⁻¹) were performed on electromechanical universal testing machine, whereas, hydro-pneumatic machine and modified Hopkinson bar apparatus were used for testing at intermediate (5 s⁻¹, 25 s⁻¹) and high strain rates (250 s⁻¹, 500 s⁻¹, 750 s⁻¹) respectively. Based on the experimental results, the material parameters of existing Cowper–Symonds and Johnson–Cook models are determined. These models fit the experimental data well in the plastic zone. The fracture surfaces of the broken specimens are studied from their fractographs taken by scanning electron microscope (SEM).     

Treatment of gaseous alpha-pinene by a combined system containing photo oxidation and aerobic biotrickling filtration

Biofiltration of hydrophobic and/or recalcitrant volatile pollutants is intrinsically limited. In the present study, a combined ultraviolet-biotrickling filter (UV-BTF) was developed to improve the removal of these compounds, and a single BTF as the control was operated under the same conditions. The experimental results showed that the UV-BTF provided higher removal efficiencies than the single BTF at an inlet concentration range of 600-1500 mg m⁻³ under shorter residence times. The maximum elimination capacities (ECs) obtained were 94.2 mg m⁻³ h⁻¹ and 44 mg m⁻³ h⁻¹ in the combined UV-BTF and single BTF, respectively. The mass ratio of carbon dioxide produced to α-pinene removed in the UV-BTF was approximately 2.74, which was much higher than that of the single BTF (1.99). Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) analysis indicated that there was more complicated microbial community in the UV-BTF than that in the single BTF. In addition, we investigated the effect of starvation or stagnation on re-acclimation and removal performance from an engineering standpoint. The results showed that the combined UV-BTF could deal with fluctuating conditions or periods without any flow (air or liquid) supply much better than the single BTF.     

Perchlorate removal in Fe0/H2O systems: Impact of oxygen availability and UV radiation

In this study, the removal of perchlorate (0.016 mM ) using Fe⁰-only (325 mesh, 10 g L⁻¹) and Fe⁰ (10 g L⁻¹) with UV (254 nm) reactions were investigated under oxic and anoxic conditions (nitrogen purging). Under anoxic conditions, only 2% and 5.6% of perchlorate was removed in Fe⁰-only and Fe⁰/UV reactions, respectively, in a 12 h period. However, under oxic conditions, perchlorate was removed completely in the Fe⁰-only reaction, and reduced by 40% in the Fe⁰/UV reaction, within 9 h. The pseudo-first-order rate constant (k₁) was 1.63 × 10⁻³ h⁻¹ in Fe⁰-only and 4.94 × 10⁻³ h⁻¹ in Fe⁰/UV reaction under anoxic conditions. Under oxic conditions, k₁ was 776.9 × 10⁻³ h⁻¹ in Fe⁰-only reaction and 35.1 × 10⁻³ h⁻¹ in the Fe⁰/UV reaction, respectively. The chlorine in perchlorate was recovered as chloride ion in Fe⁰-only and Fe⁰/UV reactions, but lower recovery of chloride under oxic conditions might due to the adsorption/co-precipitation of chloride ion with the iron oxides. The removal of perchlorate in Fe⁰/UV reaction under oxic conditions increased in the presence of methanol (73%, 9 h), a radical scavenger, indicating that OH radical can inhibit the removal of perchlorate. The removal of perchlorate by Fe⁰-only reaction under oxic condition was highest at neutral pH. Application of the Langmuir-Hinshelwood model indicated that removal of perchlorate was accelerated by adsorption/co-precipitation reactions onto iron oxides and subsequent removal of perchlorate during further oxidation of Fe⁰. The results imply that oxic conditions are essential for more efficient removal of perchlorate in Fe⁰/H₂O system.     

Effect of fluoride corrosion on the bonding strength of Ti-porcelain under static loads

The effect of fluoride corrosion on the bonding strength of Ti-porcelain under different static loads was investigated. The adhesion between the titanium and porcelain was evaluated by three-point flexure test. After being immersed in artificial saliva with pH 2.7 under 0 N, 1 N and 2 N static loads, respectively, no decrease of the bonding strength of Ti-porcelain occurred. However, the decrease of bonding strength was about 30%, 37%, and 46% after being immersed in artificial saliva with pH 2.7/F⁻ 100 ppm under 0 N, 1 N and 2 N static loads, respectively. The failure of the titanium-porcelain predominantly occurred at the titanium-oxide interface. Immersion in the artificial saliva did not affect the fracture mode of the titanium-porcelain system. The corrosion of the Ti-porcelain interface resulted in the reduction of bonding strength. The static loads enhanced the F⁻ corrosion on the Ti-porcelain interface.     

Hygroscopicity and bulk thermal expansion in Y2W3O12

Negative thermal expansion material, Y₂W₃O₁₂ has been synthesized by the solid-state method and bulk thermal expansion of the material has been investigated from 300 to 1100 K. The material reversibly forms a trihydrate composition whose X-ray diffraction pattern can be indexed to an orthorhombic unit cell with a = 10.098(1) Å, b = 13.315(3) Å, c = 9.691(4) Å. The cell volume of the hydrated pattern is 7% smaller than the unhydrated cell volume. According to the dilatometric studies, the material shows a 3-6% increase in the linear strain at about 400 K, which can be attributed to the removal of water. Sintering the material at 1473 K leads to large grain size of >100 μm, which results in a large hysteresis in the bulk thermal expansion behavior. Hot pressing at 1273 K under a uniaxial pressure of 25 MPa results in a fine-grained (2-5 μm) ceramic. Glazing the ceramic prevents moisture pick up and a linear thermal expansion over the entire temperature range 1100-300 K and an average linear thermal expansion co-efficient of −9.65 × 10⁻⁶/K is observed. The effect of water on the thermal expansion behavior of this system is discussed.     

Feasibility of nutrient recovery from industrial sludge by vermicomposting technology

Transformation of industrial sludges into vermicompost is of double interest: on the one hand, a waste is converted into value added product, and, on the other, it controls a pollutant that is a consequence of increasing industrialization. This paper reports the feasibility of utilization of vermicomposting technology for nutrient recovery from industrial sludge in laboratory scale experiment employing Eisenia fetida earthworm. A total of nine vermireactors, having different percentage of wastewater treatment plant sludge of a food industry and cow dung, were established and monitored for fertilizer quality of vermicompost and growth and fecundity of the earthworms for 3 months. The earthworms were unable to survive in 100% FIS. There was a decrease in pH, organic carbon content, organic matter, C:N ratio, and increase in ash content, EC, nitrogen, potassium and phosphorus content in all the vermireactors. Total Kjeldhal nitrogen (TKN) content increased in the range of 12.2–28.7 g kg⁻¹ in different vermireactors after vermicomposting. C:N ratio was 1.59–5.24 folds lesser in final vermicomposts than initial raw substrate. The heavy metals’ content in final vermicomposts was higher than initial feed mixtures. Maximum worm biomass was observed in control, i.e., 100% CD (836 mg earthworm⁻¹) and the lowest in 30% CD + 70% FIS feed mixture (280 mg earthworm⁻¹). Cocoon production was started during 6–7th week in all feed mixture except in feed mixture no. 9. After 12 weeks maximum cocoons (57) were counted in 100% CD and minimum (2) in 30% CD + 70% FIS feed. The results indicated that food industry sludge could be converted into good quality manure by vermicomposting if mixed up to 30% with cow dung.     

Investigation of a sewage-integrated technology combining an expanded granular sludge bed (EGSB) and an electrochemical reactor in a pilot-scale plant

A sewage-integrated treatment system (SITS) for the treatment of municipal wastewater, consisting of an expanded granular sludge bed (EGSB) reactor to remove soluble organic matter and an electrochemical (EC) reactor to oxidize the NH₃-N, was evaluated. The performance of the EGSB reactor was monitored for 12 months in a pilot-scale plant. Iron shavings were added to the EGSB reactor on the sixtieth day to improve the removal efficiency of the chemical oxygen demand (COD), suspended solids (SS) and total phosphorus (TP). After the iron shavings were added, the effluent COD, SS and TP decreased from 104 to 46 mg L⁻¹, 21 to 8.6 mg L⁻¹ and 3.62 to 1.36 mg L⁻¹, respectively. Moreover, in the EC reactor, which was equipped with IrO₂/Ti anodes, the NH₃-N and total nitrogen (TN) concentrations decreased from 25 to 12 mg L⁻¹ and 29 to 15 mg L⁻¹, respectively. The NH₃-N was directly oxidized to N₂, resulting in no secondary pollution. The results demonstrated the possibility of removing carbon and nutrients in a SITS with high efficiency. The system runs efficiently and with a flexible operation, making it suitable for low-strength wastewater. The results and parameters presented here can provide references for the practical project.     

Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor

Titanate nanotube powders (TNTPs) with the twofold removal ability, i.e. adsorptive separation and photocatalytic degradation, are synthesized under hydrothermal conditions using metal Ti particles as a precursor in the concentrated alkaline solution, and their morphology, structure, adsorptive and photocatalytic properties are investigated. Under hydrothermal conditions, the titanate nanotubes (TNTs) with pore diameter of 3-4 nm are produced on the surface of metal Ti particles, and stacked together to form three-dimensional (3D) network with porous structure. The TNTPs synthesized in the autoclave at 130 °C for 24 h exhibits a maximum adsorption capability of about 197 mg g⁻¹ in the neutral methylene blue (MB) solution (40 mg L⁻¹) within 90 min, the adsorption process can be described by pseudo second-order kinetics model. Especially, in comparison with the adsorptive and the photocatalytic processes are performed in turn, about 50 min can be saved through synchronously utilizing the double removal ability of TNTPs when the removal ratio of MB approaches 95% in MB solution (40 mg L⁻¹) at a solid-liquid (S/L) ratio of 1:8 under ultraviolet (UV) light irradiation. These 3D TNTPs with the twofold removal properties and easier separation ability for recycling use show promising prospect for the treatment of dye pollutants from wastewaters in future industrial application.     

Kinetics of the removal of mono-chlorobenzene vapour from waste gases using a trickle bed air biofilter

The performance of a trickle bed air biofilter (TBAB) in the removal of mono-chlorobenzene (MCB) was evaluated in concentrations varying from 0.133 to 7.187 g m(-3) and at empty bed residence time (EBRT) varying from 37.7 to 188.52 s. More than 90% removal efficiency in the trickle bed air biofilter was achieved for the inlet MCB concentration up to 1.069 g m(-3) and EBRT less than 94.26 s. The trickle bed air biofilter was constructed with coal packing material, inoculated with a mixed consortium of activated sludge obtained from sewage treatment plant. The continuous performance of the removal of MCB in the trickle bed air biofilter was monitored for various gas concentrations, gas flow rates, and empty bed residence time. The experiment was conducted for a period of 75 days. The trickle bed air biofilter degrading MCB with an average elimination capacity of 80 g m(-3) h(-1) was obtained. The effect of starvation was also studied. After starvation period of 8 days, the degradation was low but recovered within a short period of time. Using macrokinetic determination method, the Michaelis-Menten kinetic constant K(m) and maximum reaction rate, r(max) evaluated as 0.121 g m(-3) s(-1) and 7.45 g m(-3), respectively.     

Emissions of polycyclic aromatic hydrocarbons from fluidized and fixed bed incinerators disposing petrochemical industrial biological sludge

This study investigated the emissions of polycyclic aromatic hydrocarbons (PAHs) from two fluidized bed incinerators (FLBI_A and FLBI_B) and one fixed bed incinerator (FIBI) disposing biological sludge generated from the petrochemical industries in Taiwan. The results of 21 individual PAHs (including low (LM-PAHs), middle (MM-PAHs) and high molecular weight PAHs (HM-PAHs)) were reported. The LM-PAHs mainly dominated the total-PAHs in the stack flue gases, whereas the LM- and HM-PAHs dominated the total-PAHs in the bottom fly, fly ash and WSB effluent. Due to high carcinogenic potencies (= total-BaP_eq concentrations) in the bottom ash (195 ng g⁻¹) and WSB effluent (20,600 ng L⁻¹) of the FIBI, cautious should be taken in treating them to avoid second contamination. Lower combustion efficiency and elevated fuel/feedstock (F/W) ratio for the FIBI led to the highest total emission factor of total-PAHs (38,400 μg kg⁻¹). Lower total-PAH removal efficiencies of wet scrubber (WSB) (0.837–5.89%), cyclone (0.109–0.255%) and electrostatic precipitator (ESP) (0.032%) than those reported elsewhere resulted in high fraction in PAH contributions from the stack flue gases. Lower total-PAH emission factor was found for FLBI_A (2380 μg kg⁻¹ biological sludge) with higher combustion efficiency compared to those for FLBI_B (11,500 μg kg⁻¹) and FIBI (38,400 μg kg⁻¹ biological sludge), implying that combustion efficiency plays a vital role in PAH emissions.     

Treatment of anaerobic sludge digester effluents by the CANON process in an air pulsing SBR

The CANON (Completely Autotrophic Nitrogen removal Over Nitrite) process was successfully developed in an air pulsing reactor type SBR fed with the supernatant from an anaerobic sludge digester and operated at moderately low temperatures (18–24 °C). The SBR was started up as a nitrifying reactor, lowering progressively the dissolved oxygen concentration until reaching partial nitrification. Afterwards, an inoculation with sludge containing Anammox biomass was carried out. Nitrogen volumetric removal rates of 0.25 g N L⁻¹ d⁻¹ due to Anammox activity were measured 35 d after inoculation even though the inoculum constituted only 8% (w/w) of the biomass present in the reactor and it was poorly enriched in Anammox bacteria. The maximal nitrogen removal rate was of 0.45 g N L⁻¹ d⁻¹. By working at a dissolved oxygen concentration of 0.5 mg L⁻¹ in the bulk liquid, nitrogen removal percentages up to 85% were achieved.     

A study on crack propagation and electrical resistance change of sputtered aluminum thin film on poly ethylene terephthalate substrate under stretching

This work is designed to study crack development and resistance changes in aluminum thin films under stretching. Crack development and relative electrical resistance change (?R/R₀) of aluminum thin film on 127-μm poly ethylene terephthalate substrates were investigated as a function of engineering strain. Four thicknesses were considered for the aluminum thin films: 50, 100, 200, and 500 nm. The engineering stress-engineering strain curves were very similar for all thicknesses. Three strain rates were considered in this study: 0.1 min^− 1, 0.5 min^− 1 and 1.0 min^− 1. Before the yield point, there was no stress difference under different strain rates. However, after the yield point, stress was higher at a higher strain rate. It was found that ?R/R₀ was very sensitive to the film thickness. Optical microscope images at high magnification showed that cracks were observed at 2% strain for 100, 200, and 500 nm-thick films and at 8% strain for the 50 nm-thick films. Short lateral cracks (perpendicular to the original cracks) were observed at 20% strain for the 100 and 200 nm thick films and at 30% for the 500 nm thick films.     

Synthesis and characteristics of the C12A7-O nanoparticles by citric acid sol-gel combustion method

In this study, the O⁻-containing nanocrystal 12CaO·7Al₂O₃ (C12A7-O⁻) was synthesized by the citric acid sol-gel combustion method. The formation of the C12A7-O⁻ material was investigated via X-ray diffraction, thermogravimetric analysis, differential thermal analysis, electron paramagnetic resonance, field emission-scanning electron microscopy, and time of flight mass spectroscopy. The C12A7-O⁻ material was formed at a lower synthesis temperature (900-1150 °C), with a narrower particle size (33-74 nm). The anionic species stored in the C12A7 material was dominated by the active atomic oxygen anions (O⁻) with a concentration of (1.2 ± 0.3) × 10²⁰ cm^− 3, and the emission current density of O⁻ was about 0.89 ± 0.15 μA/cm² at T_{(sample surface)} = 800 °C and E_{(extraction field)} = 800 V/cm.     

Forming behavior and workability of 6061/B4CP composite during hot deformation

Compression tests of 6061/B₄C_P composite have been performed in the compression temperature range from 300 °C to 500 °C and the strain rate range from 0.001 s⁻¹ to 1 s⁻¹. The flow behavior and processing map have been investigated using the corrected data to elimination of effect of friction. The processing maps exhibited two deterministic domains, one was situated at the temperature between 300 °C and 400 °C with strain rate between 0.003 s⁻¹ and 0.18 s⁻¹ and the other was situated at the temperature between 425 °C and 500 °C with strain rate between 0.003 s⁻¹ and 0.18 s⁻¹.The estimated apparent activation energies of these two domains, were 129 kJ/mol and 149 kJ/mol, which suggested that the deformation mechanisms were controlled by cross-slip and lattice self-diffusion respectively. The optimum parameters of hot working for the experimental composite were 350 °C - 0.01 s⁻¹ and 500 °C - 0.01 s⁻¹. In order to exactly predict dangerous damaging mechanism under different deformation conditions exactly, Gegel’s criterion was applied to obtain processing map in the paper. The result showed that the processing map used Gegel’s criterion can be effectively to predict the material behavior of the experimental composite.     

Layered δ-MnO2 as positive electrode for lithium intercalation

Layer structured δ-MnO₂ was synthesized by a microwave-assisted hydrothermal method. The morphology of the product consists of flower-like spheres that range from about 200 nm to 3 μm in diameter and are composed of sheets about 5-10 nm in thickness. When tested in the voltage range of 2 to 4.5 V vs. Li⁺/Li in coin cells, the separator is blocked, handicapping Li⁺ conductivity and leading to cell failure. When tested in the voltage range of 2 to 4 V in ethylene carbonate/dimethyl carbonate (EC/DMC), the δ-MnO₂ delivers an initial reversible capacity of 143.7 mAh g⁻¹ and can maintain 120 mAh g⁻¹ at the 60th cycle. The δ-MnO₂ electrode shows good cycling stability at different current densities and delivers a discharge capacity of about 90 mAh g⁻¹ at 1 C, indicating that it is a promising cathode material for lithium ion batteries.     

All-organic polymer-dispersed liquid crystal light-valves integrated with electroactive anthraquinone-2-sulfonate-doped polypyrrole thin films as driving electrodes

All-organic PDLC (polymer-dispersed liquid crystal) light-valves using all-polymer conductive substrates containing thin films of polypyrrole doped with anthraquinone-2-sulfonate (AQSA⁻) as the driving electrodes were fabricated in this study. The all-polymer conductive substrates were prepared under ambient conditions by in situ depositing polypyrrole thin films on blank flexible poly(ethylene terephthalate), or PET, substrates from aqueous media in which oxidative polymerization of pyrrole was taking place. The obtained flexible all-polymer conductive substrates were semi-transparent with cohesive coatings of AQSA⁻-doped polypyrrole thin films (thickness ∼55 nm). The all-polymer flexible conductive substrates had sheet resistivity ∼40 kΩ □ ⁻¹and T% transparency against air ∼78% at 600 nm. The light-valves fabricated using the above all-polymer conductive substrates showed ∼50% transparency against air at 600 nm when 4 V μm⁻¹ electric field was applied.     

Microhardness studies on calcium hydrogen phosphate (brushite) crystals

Vicker's and Knoop microhardness studies were carried out on grown calcium hydrogen phosphate dihydrate (CaHPO₄·2H₂O) crystals over a load range of 10-50 g. The Vickers (H_V) and Knoop (H_K) microhardness numbers for the above loads were found to be in the range of 94-170 kg/mm² and 28-35 kg/mm² respectively. It was also found that these numbers increased with increase in load. The Mayer's index (n) was found to be greater than 1.6 showing soft-material characteristics. The fracture toughness values (K_c), determined from measurements of crack length, were estimated to be 6 ± 0.5 × 10³ kg m^−3/2 and 4.5 ± 0.5 × 10³ kg m^−3/2 at 25 g and 50 g respectively. The brittleness indices (B_i) were found as 2.3 ± 0.1 × 10⁴ m^−1/2 for 25 g and 3.7 ± 0.1 × 10⁴ m^−1/2 for 50 g. Using Wooster's empirical relation, the elastic stiffness coefficient (c₁₁) has been calculated from Vicker's hardness values as 4.8 ± 0.5 × 10¹⁵ Pa for 10 g, 9.7 ± 0.5 × 10¹⁵ Pa for 25 g and 13.3 ± 0.5 × 10¹⁵ Pa for 50 g. The Young's modulus was calculated as 1.5 ± 0.1 × 10¹⁰ N m⁻² from Knoop microhardness values.