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Building and Environment 39 (2004) 179 187 www.elsevier.com/locate/buildenv

Evaluation of emissions of total volatile organic compounds from carpets in an environmental chamber
H. Guoa; b ; , F. Murraya , S.C. Leeb , S. Wilkinsonc
b Research a School

of Environmental Science, Division of Science and Engineering, Murdoch University, Perth, WA 6150, Australia Centre for Urban Environmental Technology and Management, Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong c Chemistry Centre, 125 Hay Street, Perth, WA 6000, Australia Received 19 July 2002; received in revised form 6 August 2003; accepted 20 August 2003

Abstract An environmental test chamber with controlled temperature, relative humidity and air ow rate has been used to evaluate emissions of total volatile organic compounds (TVOCs) from 11 new carpets. The quantity of TVOCs emissions was measured by a gas chromatography/ ame ionisation detector. The TVOCs emissions of each product were tested as a function of time. The results showed that the time dependence of TVOCs concentrations and the change of emission rates with time can be described by a double-exponential model. With this double-exponential model, the initial emission rates (E10 and E20 ) and emission decay constants (k1 and k2 ) in evaporation- and di usion-dominated phases were simulated. These emission parameters could be used in estimation of TVOCs concentrations in an indoor environment. Model evaluation studies indicate that the Highclass carpet has the smallest model accuracy while the Double-diamond and Classic design carpets have the largest model accuracy. ? 2003 Elsevier Ltd. All rights reserved.
Keywords: Total volatile organic compounds; Environmental chamber; Carpet; Emission; Modelling

1. Introduction Carpets can be found in many houses around the world. Scientic studies have demonstrated that carpets contribute substantially to indoor air pollution by volatile organic compounds (VOCs) due to the variety and quantity of VOCs that are emitted from various products and the large area of carpets used indoors [17]. Carpets contain a multitude of synthetic compounds such as polyester, nylon, olen bres, latex and polypropylene backing [8]. Many chemicals within the carpet emit during the rst few months following installation, giving the new carpet smell [8,9]. There are over 250 gaseous compounds known to be emitted by new carpets, many of them VOCs [8]. Many of the VOCs detected are known or suspected carcinogens or irritants at high concentration levels [10]. VOCs o -gassing
Corresponding author. Research Centre for Urban Environmental Technology and Management, Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong. Tel.: +852-2766-6017; fax: +852-2334-6389. E-mail address: ceguohai@polyu.edu.hk (H. Guo).

from carpets can cause a variety of health-related symptoms, which can vary greatly from person to person. General symptoms include headaches, eye irritation, nausea, drowsiness, skin rashes and respiratory and sinus congestion [8]. In European countries and the United States, there is an interest among manufacturers of carpets in the adoption of voluntary standards where specic chemicals should not rise above specied levels. For instance, to identify carpet products which are truly low-VOC emitters, the Carpet and Rug Institute (CRI) in the USA has established a labelling program [9]. The carpet manufacturer is allowed to attach the indoor air quality label to that specic product type if the test result does not exceed the emission criteria. Since the inception of the labelling program in 1992, the industry in the USA has made substantial reductions in the emissions of total volatile organic compounds (TVOCs) from their products, as well as reductions in emissions of 4-phenylcyclohexene (4-PC). Models are needed to simulate VOC emissions from carpets, so that VOC concentrations in a real indoor environment could be predicted. Black et al. [6,11] reported

0360-1323/$ - see front matter ? 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.buildenv.2003.08.015

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that both SBR (styrene butadiene rubber) backing and non-SBR backing carpets followed rst-order decay emission proles. The rst-order decay model was also used to describe the emission process of a carpet with polyamide bres and latex backing [12]. However, the rst-order decay model was unable to explain the physical processes of the emission from carpets. Sollinger et al. [4] used a mass transfer model to describe the emission of 2,2,6,6-tetramethyl-4-methylideneheptane from an SBR backing carpet. A study by Little et al. [13] revealed that the emissions of VOCs from new carpets can be described by a di usion model. A large number of parameters in the mass transfer model and di usion model, however, were needed to be estimated or measured. Most families in Australia use carpets as oor coverings. However, there is no guideline to encourage the carpet industry to manufacture low-VOC-emitting carpets, and to assist the consumers to select the carpets, which meet the criteria for low emissions, because few data on the VOC emissions from carpets exist in Australia. Furthermore, emissions of VOCs from carpets with di erent backings have been studied in European countries and the USA. Most of these studies, however, were concentrated on the investigation of carpets with SBR backing [5]. There are no data available on the emissions of VOCs from carpets with polypropylene backing, while this type of carpet is widely used in Australia. Thus, the objectives of this study are to characterise emissions of TVOCs from carpets with polypropylene backing in order to establish a database for the evaluation of TVOCs emissions from carpets; and to obtain a variety of emission parameters from carpets using a double-exponential model.

2. Materials and methods 2.1. Materials Eleven carpets were selected based on the assessment of Australian market sales gures and use patterns. After investigation, ve 100% solution dyed olen carpets, two 100% wool carpets, one 90% wool, 10% nylon carpet, one 80% wool, 20% polypropylene carpet, one 100% nylon carpet and one 100% solution dyed nylon carpet were obtained from a local manufacturer. All carpets were manufactured with a polypropylene backing. In such carpets, the pile is xed to a support woven of polypropylene followed by the jute or synthetic backing (secondary backing). Table 1 listed the specimens tested in the study. All of the samples were immediately wrapped in Te on bags after manufacturing and were delivered to the experimental laboratory and tested within one month after supply. 2.2. Methods 2.2.1. The environmental chamber test Experiments were designed to generate TVOCs concentration data from newly applied carpet products under controlled experimental conditions in an environmental chamber. Characterisation of the environmental chamber, e.g. air mixing and leakage was detailed in our previous publication [14]. To avoid sink e ects on interior surfaces, the material used to construct the chamber must be non-adsorbent, chemically inert and with a smooth surface. In this study, glass

Table 1 Carpet samples selected for measurement Product 1. 2. 3. 4. 5. Stonegate carpet Australis carpet Double-diamond carpet Orkney carpet Contrax carpet Yarn type 100% solution dyed olen graphics Woven polypropylene 100% wool Jute Primary backing Secondary backing Jute or synthetic Pile weight (g= m2 ) 680 950 475 680 680 1360/1630 1360/1630 1360 1630 1225 815

1. Super Norsk carpet 2. Classic design carpet Dansk carpet Argyle carpet Clubclass carpet Highclass carpet

90% wool and 10% space dye nylon 80% wool and 20% synthetic 100% nylon 100% solution dyed nylon

Jute Jute Jute Synthetic

H. Guo et al. / Building and Environment 39 (2004) 179 187

181

was used. Therefore, it is justied to neglect sinks. Detailed information on this point is in report No.8 of the ECA [15]. All carpet products were tested in the glass chamber (volume: 13:56 l) with one inlet and two outlets. The cleaned chamber was placed in the temperature-controlled box. The relative humidity of the chamber air was controlled by bubbling a portion of the air stream through deionised water at a controlled temperature (in a water bath). A puried air ow of 200 ml= min was passed through the chamber. The atmosphere in the chamber was mixed by a small fan, which was suspended from the ceiling of the chamber. Before testing each carpet sample in the chamber, a chamber blank was analysed to ensure the TVOCs concentration was below 5 g= m3 . Otherwise, the chamber was cleaned again until it was qualied. The carpet samples were prepared by cutting 11:5 11:5 cm2 of carpet. Sample weight was then measured by a balance (Model 1801, Sartorius GMBH GOTTINGEN, Germany) to the nearest 0:001 g. The sample was placed in the chamber immediately after weighing. This operation was done under positive pressure from the clean air system to keep intrusion of room air to a minimum. The temperature in the chamber was set as 23 1 C; relative humidity 50 5% and air exchange rate 0:885 h1 . During the experimental period, air sample volumes of 2:0 l at a sampling rate of 200 ml= min were collected at the outlet of the chamber using Tenax-GR adsorption tube. Immediately after sampling, the tubes were tightly sealed and analysed within a few hours. Samples were collected at progressively increasing intervals. Gas chromatography/ ame ionisation detector (GC-FID) (Varian Model 3700, USA) was equipped with a modied thermal desorption cold trap injector. The samples were thermodesorbed into the GC-FID instrument for TVOCs quantitation. A lm capillary (Alltech ECONO-CAP SE-54, 30 m 0:53 mm I:D: 1:2 m) was employed for the separation of VOCs. The adsorbed sample was cryotrapped at 80 C and injected in the GC. The GC temperature program was initially 40 C for 5 min, and then increased at a rate of 5 C= min to 200 C and stayed for 3 min. The injection temperature was 200 C; the temperature of detector was 230 C. Concentration of TVOCs was calculated from the total area of the FID chromatogram using toluene response factor. By running a series of toluene standard solutions with di erent concentrations (50 g= ml500 g= ml) in GC/FID, the toluene calibration curve was obtained (R2 =0:99). Consequently, the total area of the chromatogram was converted into an equivalence of toluene. Replicate analysis of samples and standards were regularly conducted. To determine the recovery of toluene, 0:1 l of toluene was injected into the absorption tubes before thermal desorption as a quality control measure. Duplicate samples were taken to conrm sampling reproducibility.

2.2.2. Modelling of TVOCs emissions The emission rates of TVOCs from the carpet are calculated by using a double-exponential model [1517]. E (t ) = E1 + E2 = E10 ek1 + E20 ek2 ;
2
t t

(1)

where E (t ) is the emission rate of TVOCs (mg= m h), E1 the Phase 1 (evaporation-dominated) emission rate (mg= m2 h), E2 the Phase 2 (di usion-dominated) emission rate (mg= m2 h), E10 the Phase 1 initial emission rate (mg= m2 h), k1 the Phase 1 emission rate decay constant (h1 ), E20 the Phase 2 initial emission rate (mg= m2 h) and k2 the Phase 2 emission rate decay constant (h1 ). The mass balance for the chamber over a small time increment d t is Change in mass = mass emitted mass leaving chamber : This can be expressed as V d c = AE (t ) d t Qc d t;
3

(2)

where V is the Chamber volume (m ), A the sample area (m2 ), Q the ow rate through chamber (m3 = h) and c the Chamber concentration (mg= m3 ). Integrating the chamber mass balance equation (Eq. (2)) with the source term dened by Eq. (1) and assuming an initial concentration of zero gives the equation c = LE10 (ek1 eNt )= (N k1 ) +LE20 (ek2 eNt )= (N k2 );
t t

(3)

where L is the material loading (m2 = m3 ) and N = Q=V the air exchange rate (h1 ). The double-exponential model is used to analyse the chamber data using a non-linear least-squares best-t routine (MacCurveFit program). The four emission parameters E10 , E20 , k1 and k2 are then obtained. The quality of the least-squares t and the uncertainties in the coe cients are assessed automatically by the MacCurveFit program [18]. The MacCurveFit program uses an exponential peeling procedure to calculate the best estimates of the emission parameters [1820]. 2.2.3. Model evaluation The correlation between chamber measurements and emission modelling results was statistically evaluated by using techniques outlined by Stunder and Sethu Raman [21] and Hanna [22]. These techniques included both residual analysis which allows a quantitative estimate of (C p C m ) and correlation which allows a measure of agreement between measured TVOCs concentration (Cm ) and predicted concentration (Cp ). Here, C p is the mean of predicted concentrations, and C m is the mean of measured concentrations. This study used correlation coe cient (R or R2 ), an index of agreement (d) and the mean square error (MSE) to interpret model accuracy. The index of agreement can be interpreted as a measure of how an error-free model predicts a variable. MSE is composed of systematic MSEs and

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H. Guo et al. / Building and Environment 39 (2004) 179 187

50
TVOCs concentration (g/m )

unsystematic MSEu. Di erence measures provide the most rigorous and useful information regarding overall model performance. However, models contain both systematic and unsystematic errors. Systematic errors result from causes, which occur consistently. Unsystematic errors consist of a number of small e ects such as the imprecision of a constant. The best model, therefore, has a systematic di erence of zero since it should explain most of the systematic variation in observed values Cm , while the unsystematic di erence should approach the MSE. The value of MSE should be minimised so that the model is predicting at peak accuracy. A large value of MSEu may indicate that the model is as good as possible under the present conditions [21]. Therefore, the statistical descriptive relative error measure which indicates the degree to which Cp approaches Cm can then be expressed as d=1 (Cpi Cmi )2 = (|Cpi | + |Cmi |)2 ; (4)

50 Measured concentration (g/m ) 3 Modelled concentration (g/m ) 2 Modelled emission rate (g/m .h)
3

30 20 10 0 0 20 40 60

30 20 10 0

80 Time (h)

100

120

140

160

Fig. 1. The TVOCs concentration and emission rate from Stonegate carpet.

0 6 d 6 1; i = 1; 2; : : : ; n; where Cpi = Cpi C m and Cmi = Cmi C m . The index d therefore allows for sensitivity toward differences in Cm and Cp as well as proportionality changes. A value of 1.0 indicates perfect agreement between Cm and Cp values. The systematic mean square error is the error caused by model additive or proportional problems and can be expressed as MSEs = pi Cmi )2 =n (C
1= 2

i = 1; 2; : : : ; n;

(5)

pi = a + bCmi , and a and b are regression coe cients. where C The unsystematic mean square error is MSEu = pi )2 =n (Cpi C
1= 2

(6)

The total MSE is written as: MSE=(MSEs2 +MSEu2 )1=2 . In addition to MSEs, MSEu and d, calculation of summary 2 2 and Sp along with simple measures such as C m , C p , Sm 2 2 linear regression will be of use. Here, Sm and Sp are squared standard deviations for measured values and for predicted values, respectively. Hanna [22] stated that the total model error or uncertainty 2 can be dened as (Cp Cm ) , where the bar indicated an average over a certain number of pairs of Cp and Cm observed at various points and/or times. Therefore, this study also 2 evaluates the uncertainty of models by using (Cp Cm ) . 3. Results 3.1. Chamber testing 3.1.1. Hundred percent solution dyed olen carpets Five di erent types of 100% solution dyed olen carpets were measured in the environmental test chamber. Fig. 1

shows a representative graph of emission rate patterns observed. TVOC emissions from other four carpets had similar patterns and Figures are not shown here. The measured and modelled TVOCs concentrations for Stonegate carpet increased reaching a maximum of 42:3 g= m3 at 5 h and then reduced to about 14% of the maximum at 6 days (Fig. 1). The emission rate started at the maximum of 40 g= m2 h and decreased to 14% of the maximum within 6 days. Similarly, the TVOCs concentration for Australis carpet increased to a maximum in 5 h and then reduced to 1.3% of the maximum within 5 days. The maximum TVOCs concentration was 300:5 g= m3 . The emission rate started at the maximum value of 464 g= m2 h and reduced rapidly to 8.8% within 21 h and to 3% within 3 days. In the experiment with Double-diamond carpet, the TVOCs concentration reached the maximum value of 16:2 g= m3 in 3 h and reduced rapidly to 3:8 g= m3 within 7 days. The emission rate started at the maximum of 25 g= m2 h and decreased rapidly to 39% of the maximum within 2 days and to 12% within 7 days. The TVOCs concentration for Orkney carpet increased with time and reached a maximum value at 5 h and then reduced to 8% of the maximum within 5 days, respectively. The maximum TVOCs concentration was 625 g= m3 . The emission rate started at the maximum of 634 g= m2 h and reduced to 9% within 5 days. The TVOCs concentration for Contrax carpet increased to a maximum value of 603 g= m3 in 5 h and then decreased to 8:4 g= m3 within 7 days. The emission rate started at the maximum of 616 g= m2 h and reduced to 14% of the maximum within 4 days and to 3% within 7 days. 3.1.2. Hundred percent wool carpets For the 100% wool carpets, the TVOCs concentration for Super Norsk carpet increased slowly to a maximum value within 5 h and reduced rapidly to less than 3% of the maximum in 5 days (Fig. 2). The maximum TVOCs concentration was 175 g= m3 . The emission rate started at the maximum of 190 g= m2 h and decreased to 11% of the maximum within 5 days. Similarly, the TVOCs concentration for Classic design carpet increased rapidly to the maximum at 5 h and then

Emission rate (g/m .h)

40

40

H. Guo et al. / Building and Environment 39 (2004) 179 187

Measured concentration (g/m )
TVOCs concentration (g/m )
3

183
Measured concentration (g/m ) Modelled concentration (g/m ) Modelled emission rate (g/m .h)
2 3 3

50
3

50 40 30 20 10 0

200 180
TVOCs concentration (g/m )
3

Modelled concentration (g/m ) Measured emission rate (g/m .h)

2

200

Emission rate (g/m .h)

160 140 120 100 80 60 40 20 0 0 20 40 60 Time (h) 80 100 120 140 0 100

30 20 10 0 0 20 40 60 80 Time (h) 100 120 140 160

Fig. 2. The TVOCs concentration and emission rate from Super Norsk carpet.

Fig. 4. The TVOCs concentration and emission rate from Clubclass carpet (100% nylon).

Table 2 Total quantities of VOCs emitted from carpets

15
TVOCs concentration (g/m3)

Measured concentration (g/m3) Modelled concentration (g/m3) Modelled emission rate (g/m2.h)

Product
25 20

E10 =k1 (mg= m2 ) 0.36 1.96 0.01 3.32 11.4 0.005 0.01 0.01 1.42 0.01 17.68

E20 =k2 (mg= m2 ) 2.58 3.06 1.54 25.4 17.9 10.04 2.88 1.98 21.3 4.68 24.01

10 15 10 5 5 0 0 20 40 60 80 100 120 140 Time (h) 0

Emission rate (g/m2.h)

100% solution dyed olen: Stonegate Australis Double-diamond Orkney Contrax 100% wool: Super Norsk Classic design Dansk 90% wool, 10% nylon Argyle 80% wool, 20% polypropylene Clubclass 100% nylon

Fig. 3. The TVOCs concentration and emission rate from Dansk carpet (90% wool, 10% nylon).

decreased to a minimum value within a week. The modelled emission rate started at the maximum of 44 g= m2 h and reduced to 14% of the maximum within 150 h. 3.1.3. Other carpets In the experiment with 90% wool, 10% nylon carpet, the TVOCs concentration increased to a maximum of 11:8 g= m3 within 1 day and then decreased to 6:6 g= m3 within 5 days (Fig. 3). The emission rate started at the maximum of 21:6 g= m2 h and reduced to 5:7 g= m2 h within 5 days. In the 80% wool, 20% polypropylene carpet experiment, the TVOCs concentration increased rapidly to a maximum within 5 h and then decreased rapidly to 0.5% of the maximum within 96 h. The maximum TVOCs concentration was 1233:6 g= m3 . The emission rate started at the maximum of 2144 g= m2 h and then decreased to 15.8% within 22 h and to 0.04% within 5 days. The TVOCs concentration from a 100% nylon carpet increased rapidly to a maximum within 5 h and then reduced slowly to an equilibrium value within 143 h (Fig. 4). The maximum TVOCs concentration was 39 g= m3 . The modelled emission rate started at the maximum of 46 g= m2 h and decreased to 12 g= m2 h within 143 h.

Highclass 100% solution dyed nylon

The TVOCs concentration from a 100% solution dyed nylon carpet increased rapidly to a maximum value within 5:5 h and then decreased to 0.3% of the maximum within 166 h. The maximum TVOCs concentration was 1861 g= m3 . The modelled emission rate started at the maximum value of 2302 g= m2 h and reduced to 24% of the maximum within 23 h and to 0.25% of the maximum within 7 days. 3.2. Modelling The amount of TVOCs released from carpets ranged from 1.55 to 42 mg= m2 (Table 2), accounting for a small proportion of per square metre of carpets applied. The amount of TVOCs emitted in Phase 2 (E20 =k2 ) exceeded that in Phase 1 (E10 =k1 ). The squared correlation coe cients (R2 ), a measure of the degree to which the double-exponential model tted the measured concentrationtime proles, were between 0.879 and 0.992 (Table 3). The sum of squared error (SSE) ranged

Emission rate (g/m .h)

40

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H. Guo et al. / Building and Environment 39 (2004) 179 187

Table 3 Modelled emission parameters from all carpets Product 100% solution dyed olen carpet Stonegate Australis Double-diamond Orkney Contrax 100% wool carpet Super Norsk Classic design Dansk 90% wool, 10% nylon carpet Argyle 80% wool, 20% Polypropylene carpet Clubclass 100% nylon carpet Highclass 100% solution dyed nylon carpet
a Mean b Uncertainty

R2

E10 ( g= m2 h) 35:4 438:3 320a 10:0b 185:9 58:67 240:1 10:0 10:0 10:0 841:2 10:0 1609 1175

k1 (h1 ) 0:0137 0:14 0:39 0:96 0:056 0:05 0:021 1:983 1:0 0:999 0:593 0:988 0:091 0:65

E20 ( g= m2 h) 4:97 25:27 20:86 14:92 3:05 448:7 134:5 375:79 179:8 134 33:64 12:78 11:6 3:28 1302:9 158 36:02 693:8 39:2

k2 (h1 ) 0:0137 0:0129 0:009 0:0097 0:002 0:0177 0:025 0:021 0:0179 0:012 0:0117 0:004 0:0059 0:003 0:0611 0:17 0:0077 0:029 0:059

SSE

0.979 0.992 0.992 0.980 0.937 0.879 0.967 0.988 0.984 0.948 0.950

16.12 17.75 1.08 221.3 1236 228 17.67 0.913 2142 39.25 20.53

standard error of the mean. in the coe cient is not estimated due to the model limitation.

Table 4 Quantitative measures of model performance for carpets Product Summary measures Cm Stonegate carpet Australis carpet Double-diamond Orkney Contrax Super Norsk Classic design Dansk Argyle Clubclass Highclass 20.10 57.93 9.61 247.4 222.3 82.57 17.88 7.50 284.9 23.28 433.0 Cp 20.34 57.70 9.47 246.2 229.6 82.63 17.68 8.28 290.1 23.29 433.9 Sm 14.31 98.46 5.71 227.4 240.0 64.20 11.53 3.49 458.0 12.82 675.0 Sp 14.18 98.97 5.68 226.7 236.9 62.97 11.47 3.66 455.4 12.59 667.8 Model uncertainty (Cp Cm )2 2.59 2.46 0.17 247.31 1276.65 307.93 2.33 5.65 238.68 4.38 2057.37 Linear regression a 17.98 0.53 0.062 0.155 12.79 5.05 0.05 2.15 6.98 0.76 6.59 b 0.128 1.005 0.992 0.994 0.975 0.940 0.986 0.82 0.99 0.97 0.99 Di erence measures MSE 16.67 1.57 0.41 15.74 35.73 17.54 1.52 2.38 15.62 2.09 45.14 MSEs 11.85 0.52 0.15 1.85 9.20 3.66 0.25 0.99 5.98 0.40 6.79 MSEu 11.73 1.48 0.39 15.63 34.52 17.16 1.50 2.16 14.43 2.05 44.63 d 0.996 0.999 0.998 0.999 0.994 0.978 0.995 0.878 0.999 0.992 0.999

from 0.913 to 2142.2. A value of zero for SSE indicates a perfect t. Dansk 90% wool, 10% nylon carpet has a value close to zero. The Argyle 80% wool, 20% polypropylene carpet has the largest SSE value. Table 3 also indicates that the maximum emission rate from all tested specimens ranged from 21.6 to 2302 g= m2 h. The rankings of carpet products according to emission rate were Highclass 100% solution dyed nylon, 80% wool, 20% polypropylene (Argyle) Orkney, Australis and Contrax 100% solution dyed olen 100% wool (Super Norsk) 100% wool (Classic design), Stonegate and Double-diamond 100% solution dyed olens, 100% nylon (Clubclass), 90% wool, 10% nylon carpet (Dansk). To better understand about the degree of error, a listing of the various summary measures, regression coe cients and

di erence measures are presented in Table 4. The C m vs. C p summary measures indicate that on the average, the Orkney carpet under-predicts concentration values, and Contrax, Super Norsk, Argyle and Highclass carpets over-predict. The Stonegate, Australia, Double-diamond, Classic design, Dansk and Clubclass carpets predictions t the experimental values very well. A comparison of Sm and Sp gives a relative indication of how well a model is producing the observed variance. From Table 4, therefore, it seems that the Stonegate, Australia, Double-diamond, Classic design, Dansk and Clubclass carpets are best at tting the observed variability. The analysis of MSE from Table 4 indicates that the Double-diamond carpet has the least overall MSE and the Contrax and Highclass carpets have the highest overall MSE.

H. Guo et al. / Building and Environment 39 (2004) 179 187

185

The Stonegate carpet has almost the same value for MSEs and MSEu, implying that it does not t the criteria of the systematic error. The Double-diamond carpet has small SSE and the smallest systematic error. The index of agreement (d) suggests that the percentage of the potential for error in predicting concentrations have been explained by the model [21]. For the 11 products noted in Tables 2 and 3, the d values range from 0.878 to 0.999. However, interpretation of the index d should not be given too much weight since d becomes unstable when the denominator is small. 2 The values of (Cp Cm ) in Table 4 indicate that the Highclass carpet has the smallest model accuracy while the Double-diamond and Classic design carpets have the largest model accuracy. 4. Discussion This study found that the TVOCs concentrations and emission rates from carpets with polypropylene backing changed double-exponentially with time. This nding is consistent with other studies. The emission mechanisms for dry sources can be generally characterised into two types: (1) surface emission and (2) in-material transport plus surface emission. The driving forces for di usion of VOCs in a dry source are concentration gradient, pressure gradient, density gradient and temperature gradient. VOCs molecules move by molecular di usion, and/or by turbulent di usion depending on the system conditions. For VOCs transport in dry sources, molecular di usion is the dominant mechanism. A high degree of reproducibility was found between the duplicated samples for the carpets tested. The reproducibility, expressed as the di erence between duplicates divided by the mean, ranged from 4% to 8.2% for total chromatographed organics. In addition, recovery of the toluene ranged from 99% to 108% with a mean value of 103% (S:D: = 7%). In this study, the double-exponential empirical model can simply describe the degassing process without estimating or measuring a considerable number of parameters. Model evaluation indicates that the double-exponential model fairly tted the measured concentrationtime proles. The Highclass carpet has the smallest model accuracy while the Double-diamond and Classic design carpets have the largest model accuracy. The VOCs emission proles strongly depended on the generation mode and the concentration of the VOCs within the material. Free or weakly bound VOCs can be readily released from carpets into the surrounding vapour phase. The presence of temperature and vapour pressure gradients, between the surface of the carpet and overlying air enhanced the rate of release of VOCs. In carpet products, the free emission component is a characteristically short-term, high-level release compound such as unreacted formaldehyde [10]. Bound VOCs, such as formaldehyde

from N-methylol resins, can be released via hydrolytic breakdown of the polymeric structure [10]. This is a slow and continuous process and may be the source of low-level, slow decay releases. In this study, TVOCs was used as index to evaluate the characteristics of the emission from carpets. Therefore, the emission proles represented the mixture of the above two VOCs emission processes. In contrast to other materials used indoors, the emission processes from carpets are complex. The multilayering of a carpet product appears to amplify the complexity of the emission patterns. The study of Hodgson et al. [23] revealed that the dominant VOCs emitted by the carpets were, for the most part, constituents of the polymer backing materials. An experiment with one carpet, in which the bres and backing were separated and tested individually for emissions, conrmed that the backing was the dominant source [23]. A rough check of the characteristic time for a VOC to di use through a thin polymer layer appeared to conrm that the polymer backings were acting as slow di usive sources of VOCs released into the chamber air. Sollinger et al. [4] and Little et al. [13] further conrmed the nding of Hodgson et al. [23] by measuring the emission of VOCs from a carpet with a polymer backing. Both Sollinger et al. [4] and Little et al. [13] used a di usion model to explain the VOCs emissions from carpets. They assumed that the VOCs originated predominantly in a uniform slab of polymer backing material, and the transfer of an organic compound from the polymer backing through the pile into the gas phase was diffusion controlled. This study tted double-exponential transient mass-balance equations to the concentration vs. time curves for the emissions of TVOCs from eleven carpet products. Four constants were estimated for each case by nonlinear least-squares regression of a data set and close ts were obtained. However, a more rigorous validation of the model is needed to thoroughly explain the controlling mechanisms of the TVOCs emissions from carpets. Using the TVOCs decay curve data, individual products were ranked according to their total TVOCs emission amounts (measured as mg= m2 and determined over a 1-week TVOCs monitoring time) and their maximum emission rate. The data show that the TVOCs emission amounts ranged from 1.6 to 42 mg= m2 (Table 2). The Orkney carpet, Contrax carpet, 100% solution dyed nylon carpet and the 80% wool, 20% polypropylene carpet released similar amount of TVOCs in the rst week period, and the others had the similar TVOCs emission amounts. For the dry sources such as carpets, the maximum TVOCs emission rate, associated with the whole emission period of the carpet, may be used as a surrogate tool for permitting relative carpet TVOCs emission comparisons. The di erent TVOCs emissions among the carpets tested in this study are most likely to be due to the di erent generation mode of VOCs and the varied concentration of the VOCs within the carpet. Age of carpets is a critical parameter, since most materials have emission rates that vary with time. Older carpets may emit at a lower rate than new carpets; carpets stored at

186 Table 5 Emission rates for carpet products Air exchange rate (h1 ) NSa 1.0 NS 1.0 1.0 NS 0.885
a NSnot b Maximum

H. Guo et al. / Building and Environment 39 (2004) 179 187

Elapsed time after application (h) NS 24 NS NS 24 NS 168

Emission rate ( g= m2 h) 120 590 1400 45 315 6 411 5.9 82 352 698 1856 223 (Av. 14 896) 21.6 2302b

Type of carpet backing Synthetic bres Soft plastic Rubber SBR NS Latex SBR Non-SBR NS Polypropylene

Reference MHlhave [1] Black [11] Levin [24] Kirchner et al. [7] Black et al. [6] Figley et al. [25] This study

stated. emission rate.

high temperatures may also have lower emission rates when tested; and storage or transportation with other materials may cause adsorption of organics which will be re-emitted during the chamber tests. Therefore, di erent results obtained between this study and other studies may partially due to the age of carpets. The TVOCs emission rates obtained in this study (Table 5) were consistent with results of other studies, which found the TVOCs emission rates ranged from 45 g= m2 h for a SBR latex backed, nylon carpet, to 698 g= m2 h for a non-SBR backing carpet, with only a few exceptions exceeding 0:5 mg= m2 h [1,6,7,11,24,25]. Except for the purpose of obtaining the VOCs emission parameters from indoor materials, chamber experiments are intended to simulate, as much as possible, real-life situation in order to facilitate indoor concentration or exposure estimates. Black et al. [6] studied both SBR and non-SBR carpets in small and room-size environmental chambers, and reported that an excellent correlation was obtained between decay curves obtained from both types of carpet in both chambers. However, identical controlled chamber conditions were used in both chambers. In most cases, the environmental conditions between a chamber and a real house are di erent and this di erence will result in a di erence of TVOCs concentrations. Therefore, when the chamber concentrations of TVOCs are used to predict an indoor air quality, the TVOCs concentrationtime proles in the chamber can be mathematically modelled to derive emission rates of TVOCs. These model-derived emission parameters, associated with air temperature, air velocity, relative humidity, and material loading could then be used to evaluate TVOCs concentrations in a real house.

ral change of TVOCs concentrations and emission rates in the test chamber presented a good t with the results from a double-exponential model. The double-exponential model provided reliable estimates of the initial emission rate, maximum TVOCs concentration, mass of TVOCs released, and other emission parameters. Model evaluation studies indicated that the Highclass carpet had the smallest model accuracy while the Double-diamond and Classic design carpets had the largest model accuracy. Acknowledgements The authors would like to thank Mr. Kelvin Maybury for his technical assistance in this study. References
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5. Conclusion Environmental chamber tests showed di erences in rates and patterns of TVOCs emissions from carpets. The tempo-

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