Determination of the complexing properties of drinking waters toward copper(II) and aluminium(III) by ligand titration

The complexing capacity of some drinking waters for aluminium(III) and copper(II) is determined by a ligand titration with metal ions based on the use of complexing resins. The resins used in the titration are the iminodiacetic resin Chelex 100, the carboxylic resin Amberlite CG50 and the anionic exchange resin AG1X8. They allow the detection of ligands forming complexes of different stability with the metal ions used for the titration, since they have different sorbing properties. After equilibration with the resin, the concentration of the free metal ion in solution is evaluated from the concentration of sorbed metal ion and from the quantity K^*, which is the ratio of the concentration of the metal ion sorbed on the resin to the free metal ion in solution. It strongly depends on the conditions, but it can be evaluated, at the considered conditions, from the sorption equilibria of the metal ion on the resin. The concentration of the ligands in solution and the conditional stability constant are obtained from the Ruzik linearization procedure. Very strong ligands of copper(II) and aluminium(III) were detected in a tap water sample at concentrations ranging from 10⁻⁷ to 10⁻⁶ mol kg⁻¹, and forming complexes having conditional complexation constants K_cI=2.3×10¹⁷ (pH=6.77) and 4.5×10¹⁶ (pH=6.24), respectively, for copper(II) and aluminium(III). Weaker ligands were detected using the less strongly sorbing resins Amberlite CG50 and AG1X8, but at a concentration equal to that of the strong ligands. This was ascribed to the presence of competing metals in solution, not sorbed by the weak resins. Two other drinking waters had completely different complexing properties both towards copper(II) and aluminium(III), containing much weaker ligands.     

Complexation of copper in the effluent of a sewage treatment plant and an estimate of its influence on toxicity to coho salmon

Measurements by cupric ion electrode of the complexing capacity of the effluent from a sewage treatment plant (STPE) averaged 0.300 mg 1⁻¹. Of the complexed Cu 67% was due to compounds of 10,000 MW. Organic compounds removable by activated carbon composed 88% of the total organic carbon and were responsible for 87% of the complexation. Complexation of Cu²⁺ by STPE diminishes the toxicity from total Cu to juvenile coho salmon; the LC₅₀ was 0.164 mg 1⁻¹ for river water vs 0.286 mg 1⁻¹ for 40% STPE. The LC₅₀ of Cu²⁺ was approximately the same (0.017 vs 0.022 mg 1⁻¹) in both matrices; this species thus appears to play a toxic role. The mean survival time in diluted STPE with added Cu was inversely proportional to the Cu²⁺ concentration.     

Kinetics of alachlor transformation and identification of metabolites under anaerobic conditions

Alachlor is one of the two most commonly used herbicides in the United States. In the environment, little mineralization of this compound has been found to occur, and metabolites of alachlor may be formed and could accumulate. The objectives of this study were to determine the rate of alachlor biotransformation and to identify the transformation intermediates formed under aqueous denitrifying, methanogenic, and sulfate-reducing conditions. Second-order biotrasnformation coefficients for alachlor were determined to be 7.6 × 10⁻⁵ (±4.0 × 10⁻⁵), 2.9 × 10⁻³ (±1.6 × 10⁻³), and 1.5 × 10⁻² (±1.4 × 10⁻²) 1 mg VSS⁻¹ day⁻¹ under denitrifying, methanogenic, and sulfate-reducing conditions, respectively. Acetyl alachlor and diethyl aniline were positively identified as transformation products of alachlor under all conditions. In denitrifying reactors aniline was identified as a product of alachlor. When acetyl alachlor was fed as the parent compound, aniline was also identified as a transformation product under methanogenic conditions. This research showed that although alachlor is degraded under denitrifying, methanogenic, and sulfate-reducing conditions, significant concentrations of several metabolites are formed and are only slowly degraded.     

Sorption of cadmium(II) and zinc(II) ions from aqueous solutions by cassava waste biomass (Manihot sculenta Cranz)

The sorption of two divalent metal ions, Cd(II) and Zn(II), onto untreated and differentially acid-treated cassava waste biomass over a wide range of reaction conditions was studied at 30°C. The metal ion removal from the spent biomass was also measured. The batch experiments show that pH 4.5–5.5 was the best range for the sorption of the metal ions for untreated and acid-treated biomass. Time-dependent experiments for the metal ions showed that for the two metals examined, binding to the cassava waste biomass was rapid and occurred within 30 min and completed within 1 h. High sorption capacities were observed for the two metals. The binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 86.68 mg/g Cd, 55.82 mg/g Zn and 647.48 mg/g Cd, 559.74 mg/g Zn for untreated and acid-treated biomass, respectively. It was further found that the rate of sorption was particle-diffusion controlled, and the sorption rate coefficients were determined to be 2.30×10⁻¹ min⁻¹ (Cd²⁺), 4.0×10⁻³ min⁻¹ (Zn²⁺) and 1.09×10⁻¹ min⁻¹ (Cd²⁺), 3.67×10⁻² min⁻¹ (Zn²⁺) for 0.5 and 1.00 M differential acid treatment, respectively. Desorption studies showed that acid treatment inhibited effective recovery of metal ions already bound to the biomass as a result of stronger sulfhydryl-metal bonds formed. Less than 25% of both metals were desorbed as concentration of acid treating reagent increases. However, over 60% Cd and 40% Zn were recovered from untreated biomass during the desorption study. The results from these studies indicated that both untreated and acid-treated cassava waste biomass could be employed in the removal of toxic and valuable metals from industrial effluents.     

Manufacturing effects on the hydraulic properties of needlepunched nonwoven geotextiles

Needlepunched nonwoven geotextiles are entangled to form a complex three-dimensional structure by random fibers, accounting for its bulky nature, wide range of pore size distribution, and good drainage. With needlepunched nonwoven geotextiles, water can move in both the vertical and horizontal directions. This paper examines two types of needlepunched nonwovens: one produced from polyester staple fiber and the other made from polyester spunbond continuous filaments. Experimental results indicate that the permittivity of staple needlepunched nonwoven geotextiles varies from 1.77-4.51 s⁻¹; the permeability coefficient varies from 0.63-2.87 × 10⁻² m/s. The permittivity of spunbond needlepunched nonwoven geotextiles varies from 1.13-1.97 s⁻¹; the permeability coefficient varies from 0.48-1.09 × 10⁻² m/s. In addition, the transmissivity of needlepunched nonwoven geotextiles decrease to an essentially constant value as the normal stress is increases. The transmissivity of needlepunched nonwoven geotextiles examined varies from 155-2.75 × 10⁻⁶ m²/s over the normal stress range examined (5-200 kN/m²). The AOS value of 3 denier staple fiber needlepunched nonwovens is less than 0.074 mm, the AOS value of spunbonded 7 denier and, 15 d and 20 d needlepunched nonwovens are 0.21 mm, 0.25 mm and 0.30 mm, respectively.     

Histological and toxicological responses of the mummichog, Fundulus Heteroclitus (L.) to combinations of levels of cadmium and dissolved oxygen in a freshwater

Impact of dissolved oxygen concentration (D.O.) on toxicity of cadmium to mummichogs in a freshwater medium and histological changes associated with exposure were determined. Levels of mortality were related to duration of exposure, cadmium concentration, and levels of dissolved oxygen. Median tolerance concentrations, at 96h, ranged upward from 1.3 to about 3.0 mg Cd 1⁻¹ at 2.3 and 8.5 mg DO 1⁻¹, respectively. Statistical analyses of mortality data showed factors examined were interdependent and that Cd × DO and Cd × time interactions were significant (P < 0.01). No histopathology was evident at 3 mg Cd 1⁻¹, although histopathology was evident in gills from fish exposed to 28 mg Cd 1⁻¹ for 6 1/2 h.

Responses of mummichogs to cadmium in freshwater are compared with results of a previous study involving exposure of the species to cadmium in seawater and with responses of freshwater fishes subjected to various heavy metals. Differences and similarities in patterns of response are discussed in terms of water balance.     

Recovery of ammonia from industrial waste water

Some types of industrial waste water contain high concentration of ammonia, which makes nitrification too costly. It has been found, that ion exchange is an attractive alternative, even the waste water contains such high concentration of competitive ions at 1 g 1⁻¹ Ca²⁺ and 5 g 1⁻¹ Na⁺. However it was found, that the pH increased during the treatment due to the release of OH^- ions left in the interstitial water. Since it is essential for the efficiency that pH is 7·0 or lower, it was necessary to rinse the ion exchangers with acid. The observed data by column experiments agree with the equilibrium data found.     

Hypolimnetic aeration and dissolved gas concentrations: Enclosure experiments

Two large circular enclosures, each containing approx. 550 m³ of water, 14 m deep, and open to the mud-water interface, were used to monitor the effects of hypolimnetic aeration. One enclosure was held as a control, the other aerated every 3 or 4 days for a period long enough (usually < 2 h) to maintain hypolimnetic O₂ levels at > 4 mg 1⁻¹. Nutrient additions (10 g of 90% H₃ PO₄ and 250 g NaNO₃ per week) to each enclosure were controlled from the commencement of the experiment (17 June 1980) until its completion (2 November 1981). Temperatures in both enclosures were identical. Hypolimnetic O₂ levels in the control fell to zero during both summers, but remained at > 4 mg 1⁻¹ in the aerated enclosure. Free N₂ concentrations in the hypolimnion of the aerated enclosure was higher than in the control. Concentrations of H₂S in the control hypolimnion increased to > 5 mg 1⁻¹ and concentrations of CH₄ increased to > 18 mg 1⁻¹. Both remained at or near zero in the aerated enclosure. Tests of aerator efficiency suggested that the full air-lift design that was employed had an average O₂ exchange efficiency of 42% which is higher than the values reported for most other designs.     

Mechanisms and products of ozonolysis of aniline in aqueous solution containing nitrite ion

The presence of nitrite ions (1 × 10⁻⁴ M) in the reaction medium affected the aqueous reaction of aniline (1 × 10⁻⁴ M) and ozone (2.07–2.15 × 10⁻⁴ M) at pH 6.25–10.65; o-, m- and p-nitroaniline were formed in addition to reaction products reported earlier. The combined yield of o- and p-nitroaniline was as high as 8%. Their yields were significantly higher at pH 6.25 and 7.25 than at pH 10.65 and carbonate species-inhibited their formation. The reaction mechanisms for the formation of the nitroanilines involves pernitrous acid, hydroxyl radical and nitrogen dioxide radical as the important intermediates.     

Effect of exposure time and copper concentration on reproduction of the fathead minnow (Pimephales Promelas)

Three concurrent studies were conducted to determine the chronic effect of prespawning exposure to various concentrations of copper on fathead minnow reproduction. Copper was introduced into the three exposure systems to give 6-, 3-, and 0-months exposure prior to spawning. Prespawning exposure time had no significant effect on reproduction. Number of eggs produced per female decreased, however, with increase in copper concentrations. Egg production at copper concentrations of 37μg 1⁻¹ and higher was significantly lower (P = 0.05) than in the control, but at concentrations of 24μg 1⁻¹ and lower it was not different. The maximum acceptable toxicant concentration (MATC) was estimated to be 32μg Cu 1⁻¹, which is 0.07 of the 96h LC₅₀. This application factor for copper is similar to those found in other studies.     

Characterization of copper complexation with natural dissolved organic matter (DOM)--link to acidic moieties of DOM and competition by Ca and Mg

We investigated Cu complexation by three dissolved organic matters (DOMs) collected by reverse osmosis (RO). Alkalimetric titration, pH-stat Cu and Ca titrations, pH edges of Cu–DOM complexation, and Ca/Mg–Cu exchange experiments were investigated at I=10⁻² M for DOM samples of 10 mg C/L. The proton and Cu binding characteristics indicated similarity for all three DOMs. All Cu titrations employed ion selective electrode measurement and indicated the presence of relatively small amounts of strong Cu-binding sites. Four distinct classes of Cu binding sites are required for FITEQL 4.0 to provide good fits to the entire curves. The estimated total Cu binding site density is 4.55 mmol/g C, much less than the total acidity but very close to the phenolic site content. Cu–DOM complexation increases approximately 10-fold per pH unit, even at relatively high pH (>8). We suggest that sites characterized as phenolic based on alkalimetric titration, not carboxyl sites, account for the majority of Cu complexation under natural water conditions, and Cu–DOM complexation is principally through the replacement of H⁺ by Cu²⁺ at the phenolic binding sites. The Cu–H exchange ratio is 1:1 for the first three sites and about 1:2 for the 4th site. This 4-site model describes well the pH dependency of Cu–DOM complexation and provides good estimates of free Cu concentrations throughout wide total copper (Cu_T) and pH ranges. Comparison between Ca–DOM and Cu–DOM complexation demonstrated that (i) Ca–DOM complexation increases much less than an order of magnitude per pH unit and decreases at higher Ca concentration, different from that of Cu–DOM complexation; and (ii) Cu–DOM complexation is highly non-linear, in contrast to the much reduced extent of non-linearity of Ca–DOM complexation. Ca/Mg–Cu exchange experiments showed small competition effect, less than expected by a simple competition model, and the competition tended to reduce with increasing Ca or Mg concentrations. The extent of the competition by Mg and Ca are essentially comparable. Put all together, it suggests that Ca and Mg are preferably bound by carboxyl sites, especially at relatively high concentrations, resulting in a weakened apparent competition effect.     

Fe(III) homogeneous photocatalysis for the removal of 1,2-dichlorobenzene in aqueous solution by means UV lamp and solar light

Chlorinated hydrocarbons are widely used in chemical industries as solvents and intermediates for pesticides and dyes manufacture. Their presence was documented in rivers, groundwaters and seawaters.

In this work, the oxidation of 1,2-dichlorobenzene in aqueous solutions by means of Fe(III) homogeneous photocatalysis under UV lamp and sunlight irradiations is studied. The results show that the best working conditions are found for pH=3.0 and initial [Fe(III)] concentration equal to 1.0×10⁻⁴ mol L⁻¹ although the investigated system can be utilized even at pH close to 4.0 but with slower abatement kinetics.

Some dicholoroderivatives, such as 2,3-dichlorophenol, 3,4-dichlorophenol and 2-chlorophenol, are identified as oxidation intermediates. The values of the kinetic constant for the photochemical reoxidation of Fe(II) to Fe(III) are evaluated by a mathematical model in the range 1.58–3.78 L mol⁻¹ s⁻¹ and 0.69–0.78 L mol⁻¹ s⁻¹ for the systems irradiated by UV lamp and sunlight, respectively.     

Uptake and release of phosphate by a pure culture of Acinetobacter calcoaceticus

Uptake and release of phosphate by a pure culture of Acinetobacter calcoaceticus were investigated under aerobic and anaerobic conditions. The total phosphorus content of this bacterium varied from 0.3 to 1.7 mmol g⁻¹ dry cells or from 0.93 to 5.3% of dry cell weight under various culture conditions. The log-phase cells accumulated polyphosphates of 0.33−0.64 mmol P g⁻¹ dry cells. ³¹P NMR spectra suggested that a portion of polyphosphates was likely bonded to some sort of structural components of the cell. A. calcoaceticus release phosphate linearly with time when transferred from aerobic to anaerobic conditions. The release rate was in the range of 5.9–14.7 × 10⁻³ mmol P g⁻¹ dry cells h⁻¹ and about 4–8% of cellular phosphorus was released during the initial 6 h. During the process of phosphate release acetate was not taken up by this bacterium.     

A kinetic study of 3-chlorophenol enhanced hydroxyl radical generation during ozonation

Hydroxyl (OH) radical is proposed as an important factor in the ozonation of water. In the present study, the enhancing effect of 3-chlorophenol on OH radical generation was mathematically evaluated using electron spin resonance (ESR)/spin-trapping technique. OH radical was trapped with a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a stable adduct, DMPO–OH. The initial velocity of DMPO–OH generation in ozonated water containing 3-chlorophenol was quantitatively measured using a combined system of ESR spectroscopy with stopped-flow apparatus which was controlled by home-made software. The initial velocity of DMPO–OH generation increased as a function of the concentration of ozone and the more effectively of 3-chlorophenol concentration. The relation among ozone concentration, amount of 3-chlorophenol and the initial velocity (ν₀) of DMPO–OH generation was mathematically analyzed and the following equation was obtained, ν₀ (10⁻⁶M/s)={9.7×[3-chlorophenol (10⁻⁹M)]+0.0005} exp(57×[ozone (10⁻⁹M)]). The equation fitted very well with the experimental results, and the correlation coefficient was larger than 0.99. The equation for the enhancing effect by 3-chlorophenol should provide useful information to optimize the condition in ozone treatment process of water containing phenolic pollutants.     

Growth of Selenastrum capricornutum in natural waters augmented with detergent products in wastewaters

A determination of whether the removal of phosphate builders from detergents would modify the ability of domestic secondary treated sewage effluent to stimulate the growth of a test alga (Selenastrum capricornutum-Printz) in receiving waters alone and augmented with detergent products was made. The lakes used as sources of test waters were located in northeastern New York State and possessed total phosphorus concentrations ranging from ca. 0.01 to 0.04 mg P1⁻¹.

The alga experienced stimulation in all three test lake waters from secondary sewage containing detergent with phosphate or detergent without phosphate. A concentration of 60 μg P 1⁻¹ was sufficient to effect significant algal growth in two of the test waters; however, concentrations ranging up to 110 μg P 1⁻¹ did not generate such a response in the third test water. This latter result and others suggested that neither phosphorus nor other nutrients from these wastewater additions were the factors fully accountable for the observed response(s).     

Toxicity of chlorine to juvenile spot, Leiostomus Xanthurus

The sensitivity of juvenile spot, Leiostomus xanthurus, to total residual chlorine (TRC) in flowing sea-water was investigated. Incipient LC₅₀ bioassays, histopathology, avoidance tests and the combined effect of thermal stress and TRC were used to assess sensitivity.

Estimated incipient LC₅₀ values were 0.12 mg 1⁻¹ TRC at 10°C and 0.06 mg 1⁻¹ TRC at 15°C. Histological examination of spot used in the incipient LC₅₀ bioassay at 15°C and sacrificed while alive indicated pseudobranch and gill damage occurred in individuals exposed to a measured TRC concentration of 1.57 mg 1⁻¹. Spot exposed to lower concentrations of TRC, 0.02 0.06 mg 1⁻¹ at 15°C and sacrificed alive showed no consistent tissue damage.

Spot demonstrated temperature dependent avoidance responses to TRC. At 10°C, a concentration of 0.18 mg 1⁻¹ was required for significant (X²; P < 0.05) avoidance; at 15 and 20°C, spot showed significant avoidance of TRC concentrations as low as 0.05 mg 1⁻¹.

Simultaneous exposure of spot to thermal stress (5, 10 or 13°C above the acclimation temperature of 15°C) at measured TRC concentrations of 0.05 0.07 and 0.34–0.52 mg 1⁻¹ demonstrated a significant, (Z²) with Yates correction, P < 0.05) increase in sensitivity to TRC with increased temperature and exposure times for some of the groups tested.     

Relating seismic velocities, thermal cracking and permeability in Mt. Etna and Iceland basalts

We report simultaneous laboratory measurements of seismic velocities and fluid permeability on lava flow basalt from Etna (Italy) and columnar basalt from Seljadur (Iceland). Measurements were made in a servo-controlled steady-state-flow permeameter at effective pressures from 5–80 MPa, during both increasing and decreasing pressure cycles. Selected samples were thermally stressed at temperatures up to 900 °C to induce thermal crack damage. Acoustic emission output was recorded throughout each thermal stressing experiment.

At low pressure (0–10 MPa), the P-wave velocity of the columnar Seljadur basalt was 5.4 km/s, while for the Etnean lava flow basalt it was only 3.0–3.5 km/s. On increasing the pressure to 80 MPa, the velocity of Etnean basalt increased by 45%–60%, whereas that of Seljadur basalt increased by less than 2%. Furthermore, the velocity of Seljadur basalt thermally stressed to 900 °C fell by about 2.0 km/s, whereas the decrease for Etnean basalt was negligible. A similar pattern was observed in the permeability data. Permeability of Etnean basalt fell from about 7.5×10⁻¹⁶ m² to about 1.5×10⁻¹⁶ m² over the pressure range 5–80 MPa, while that for Seljadur basalt varied little from its initial low value of 9×10⁻²¹ m². Again, thermal stressing significantly increased the permeability of Seljadur basalt, whilst having a negligible effect on the Etnean basalt. These results clearly indicate that the Etnean basalt contains a much higher level of crack damage than the Seljadur basalt, and hence can explain the low velocities (3–4 km/s) generally inferred from seismic tomography for the Mt. Etna volcanic edifice.     

Fish toxicity of jet fuels—I. The toxicity of the synthetic fuel JP-9 and its components

The toxicity of the jet fuel JP-9 and its components RJ-4, RJ-5 and MCH was assessed in static bioassays on the warm water fish, golden shiner (Notemigonus chrysoleucas). The 96-h LC₅₀ of emulsions was 2.0 mg 1⁻¹ for JP-9, 0.51 mg 1⁻¹ for RJ-4, 0.61 mg 1⁻¹ for RJ-5 and 72 mg 1⁻¹ for MCH. As determined by the 96-h LC₅₀ values unemulsified fuel (pools of fuel) JP-9 was 235 times less toxic, RJ-4 was 196 times less toxic, RJ-5 was 7700 times less toxic and MCH was 3.3 times less toxic than the corresponding emulsified materials.

In continuous flow bioassays with the water soluble fraction of the fuel and its components the effect on egg hatchability and fry development of flagfish (Jordanella floridae) and rainbow trout (Salmo gairdneri) was studied. The no effect of level on flagfish egg hatchability was 0.23 mg 1⁻¹ for JP-9 and 0.05 mg 1⁻¹ for RJ-5. Concentrations of 0.83 mg 1⁻¹ MCH and 0.2 mg 1⁻¹ RJ-4 did not affect egg hatchability. In rainbow trout studies 97-day LC₅₀ values for RJ-4 and RJ-5 were 0.045 mg 1⁻¹ and 0.072 mg 1⁻¹, respectively, and 23-day LC₅₀ values for JP-9 and MCH were 0.26 mg 1⁻¹ and 1.3 mg 1⁻¹, respectively.

The accumulation of fuels in fish bodies was studied and it was found that flagfish can tolerate a total body burden of 0.5 mg MCH g⁻¹ wet weight without lethality. It was also found that body burdens of 0.43 mg RJ-4 g⁻¹ and of 0.27 mg RJ-5 g⁻¹ on a wet weight basis will produce 50% mortality in rainbow trout.

Voiding of MCH from fish bodies occurs readily in fuel-free water, but RJ-4 and RJ-5 are retained in the tissues.     

Toxicities of total and chelex-labile cadmium to salmon in solutions of natural water and diluted sewage with potentially different cadmium complexing capacities

The LC₅₀ for total Cd averaged 4.8 and 8.0 μg1⁻¹ in river water and 33% sewage-treatment-plant effluent (STPE), respectively, and for Chelex-labile Cd, 3.9 and 5.6 μg1⁻¹, respectively. The LC₅₀ values for total Cd were significantly (P < 0.05) different, indicating a reduction in toxicity of Cd in the presence of 33% STPE, presumably due to complexation of Cd²⁺. The similarity of LC₅₀ values for Chelex-labile Cd indicates that that fraction contained toxic species of Cd at approximately the same concentration(s) in both river water and 33% STPE; it is therefore considered a better measure of Cd toxicity than total Cd. Furthermore, mortality was correlated with the concentration of Chelex-labile Cd but not with that of Chelex-nonlabile Cd. Measurements of Cd²⁺-complexing capacity by the Chelex method indicated that toxicity was due, at least in part, to Cd²⁺. Values were less than those obtained by the ion-selective-electrode method; these indicated that toxicity was due only to complexed Cd. Values from both methods were uncorrelated with LC₅₀ values.     

Influences of sample thickness on the early transient stages of concurrent flame spread and solid burning

The effects of solid thickness on the initial stages of concurrent flame spread are studied through numerical simulation. The two-dimensional mathematical formulation of the problem is based on the fully elliptic, reactive Navier-Stokes equations coupled to energy and mass conservation equations for a charring solid. For all fuel thicknesses, uniform burn-out, pyrolysis and flame propagation rates are approached after an accelerative stage. As with the opposed flow problem, three main regimes of spread rate are established based on the dependence on fuel thickness. The first (kinetic) regime, where spread rates increase with the thickness, is established for samples below 0.008 × 10⁻² m. Both flame and pyrolysis lengths are very short. In the second (thermally thin) regime, the spread rates decrease as the solid thickness is increased while the flame and the pyrolysis regions become successively larger. Finally, as the fuel thickness is increased above 0.5 × 10⁻² m, the thermally thick regime, signified by constant spread rates, is simulated. As no experimental measurements of spread rate dependency on the thickness of charring materials are available, numerical predictions are compared with a thermal theory to assess its validity limits.