Identification of chemical substances in industrial wastes and their pyrolytic decomposition products

Chemosphere 59 (2005) 1343–1353 www.elsevier.com/locate/chemosphere

Identification of chemical substances in industrial wastes and their pyrolytic decomposition products Seiichi Ishikawa *, Yoshio Sakazaki, Yoshio Eguchi, Ryoji Suetomi, Etsuko Nakamura Aqua Research Center, Kitakyushu City Institute of Environmental Sciences, Shinike 1-2-1, Tobata-ku, Kitakyushu 804-0082, Japan Received 19 June 2003; received in revised form 22 November 2004; accepted 22 November 2004

Abstract In order to quantify the sources of chemical pollutants in the leachate from reclaimed wastes, chemical substances in 11 different types of industrial wastes were identified. Their elution behaviors were also investigated. Alkanes (5.3– 890 ng g 1), benzenes (8.1–110 ng g 1), polyaromatic hydrocarbons (PAHs) (3.2–560 ng g 1), alcohols, steroids, phenol (7.1 ng g 1), ketones, furans (190–210 ng g 1), phthalates (8.9–560 ng g 1), benzoquinones, dibenzothiophene (190 ng g 1), benthiocarb (4.2 ng g 1), sulfur, nitrile compounds, amino compounds, amido compounds, pyridines, quinolines (1.8–15 ng g 1), isoquinolines, carbazoles, acridines, chlordenes (1.5–1.6 ng g 1) and nonachlors (1.1– 1.6 ng g 1) were detected in 9 types of industrial wastes. The chemical substances detected in waste at the highest concentrations were alkanes, PAHs and phthalates. Water supply sludge, dust and brick garbage contained many kinds of chemical substances. The elution behaviors of specific chemical substances, COD and nutrients varied by characteristic and production process of each waste. Over 100 different compounds were detected in pyrolysis products including carbohydrate, carotynoid, amino acids, proteins, humic acids, lignin and combustion products.
2004 Elsevier Ltd. All rights reserved. Keywords: Industrial wastes; Chemical substances; GC/MS; Pyrolysis; Elution test

1. Introduction The pollution of ground and surface waters (Coleman et al., 1980; Nakasugi, 1993; US EPA, 1993) with the toxic substances in the leachate from reclaimed wastes has become a serious problem. Moreover, Bram*

Corresponding author. Tel.: +81 93 882 0333; fax: +81 93 871 2535. E-mail address: [email protected] (S. Ishikawa).

lett et al. (1987) report that only 4% of organic compounds were identified in the leachates from 13 reclaimed waste sites in USA. Knowledge of the content and the elution behavior of toxic substances in waste is important. Though there are many reports on the toxic substances in the leachate (Reinhard et al., 1984; Lema et al., 1988; Brown et al., 1989; Yasuhara et al., 1992; Yasuhara, 1995) or the inorganic compounds in wastes (Francis and White, 1987; Sakai et al., 1991; Aoi et al., 2002), there are a few reports on chemical substances in the treated wastes and their behaviors. We quantified

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2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2004.11.046

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the chemical substances in 11 types of industrial wastes and investigated their elution behaviors. We also identified the chemical substances produced by the pyrolyses of those wastes to investigate their organic components, which were related to the elution behaviors of chemical substances and generated the new pollutants.

2. Material and methods 2.1. Instruments Gas chromatograph–flame photometric detector (GC–FPD) and GC–flame thermionic detector (GC– FTD) and gas chromatograph/mass spectrometer (GC/ MS) were a Hewlett Packard HP-5890 series and a Finnigan MAT ITOS magnum, respectively. Pyrolyzer/ GC–flame ionization detector (GC–FID) was a Shimadzu PYR-2A/GC-9A. Total organic carbon (TOC) analysis and total nitrogen (T-N) analysis were performed using a Shimadzu TOC-5000 and a Yanaco TN-7, respectively. 2.2. Reagents Standard reagents of chemical substances were obtained from Tokyo Kasei Kogyo Co., Nacalai Tesque

INC. and Wako Pure Chemical Industries. Naphthalene-d8 and phenanthrene-d10 were obtained from Kanto Chemical Co. All solvents were the grade reagents for pesticide residue analysis, which were obtained from Kanto Chemical Co. and Wako Pure Chemical Industries. Other reagents were special grade reagents, which were obtained from Wako Pure Chemical Industries. One molar H2SO4 solution, 30% NaOH solution and 2% NaCl solution were washed with n-hexane twice before use. Alumina and silica gel column chromatography was performed using a Waters Sep-pak Plus Alumina N Cartridge and a Waters Sep-pak Plus Silica Cartridge. Both Sep-paks were washed with 50 ml of acetone and 20 ml of n-hexane, in turn, before use. Anhydrous Na2SO4 and NaCl was heated at 800 C for 3 h after acetone-washing. The water was purified using a Millipore Milli-Q Ultra-pure Water System. 2.3. Samples Eleven different industrial wastes (Table 1) were collected for the study. These included materials from a municipal landfill, sludge A, B and C from a concrete factory, a chemical building materials factory and an inorganic chemical industrial goods factory. Sludge D– F were those of coagulation sedimentation at the 3

Table 1 Industrial wastes used for this experiment Moisture content (%)

ILa (%)

Humic acids (mg g 1)b

Hum/IL (%)

A B C D E F G H I J K L M N O P Q R S

16.9 ± 1.1 44.7 ± 5.1 48.8 ± 4.5 41.6 ± 7.3 40.6 ± 5.8 71.2 ± 6.2 27.3 ± 2.1 22.2 ± 1.5 8.3 ± 0.9 2.9 ± 0.5 6.1 ± 0.8 17.4 ± 0.4 4.0 ± 0.3 0.4 ± 0.1 0.2 ± 0.1 0.0 ± 0.0 1.3 ± 0.4 2.1 ± 0.5 27.9 ± 1.2

2.4 ± 0.6 27.5 ± 3.1 70.2 ± 5.8 45.2 ± 8.3 68.0 ± 5.0 37.4 ± 6.2 14.0 ± 2.6 50.0 ± 3.9 1.4 ± 0.2 1.8 ± 0.2 3.1 ± 0.5 4.8 ± 0.3 0.2 ± 0.1 1.1 ± 0.2 0.3 ± 0.1 0.0 ± 0.0 16.1 ± 5.8 58.0 ± 10.2 6.0 ± 0.3

0.00 ± 0.00 0.00 ± 0.00 0.03 ± 0.01 0.89 ± 0.10 0.00 ± 0.00 0.80 ± 0.12 0.00 ± 0.00 1.60 ± 0.46 – – – – – – – – 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00

0.000 0.000 0.004 0.197 0.000 0.215 0.000 0.320 – – – – – – – – 0.000 0.000 0.000

T

9.9 ± 1.0

5.9 ± 1.3

0.00 ± 0.00

0.000

U V

52.9 ± 5.3 59.6 ± 7.3

16.5 ± 1.5 20.5 ± 2.3

4.97 ± 1.28 3.51 ± 1.05

3.01 1.71

Industrial waste Sludge

Sludge (water supply)

Cinder Dust Slag

Cast sand Garbage (metal) Garbage (glass and pottery) Garbage (brick) Press soil Industrial waste of Cabinet Order No. 13 Sea sediment

Mean ± SD (n = 3). a % Ratio of reduced weight to dry sample weight after 1 h ignition at 600 ± 25 C. b The weight is based on dry weight.

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municipal water purifying plants. Cinder G and dust H were those from the incinerators at a waste treatment facility and a soda and chlorine compounds factory, Slag I–M and cast sand N–O were those from the 7 metal goods or machine and tools factories. Garbage P, Q and R were the metal garbage from a metal goods factory, the glass and pottery garbage from an inorganic chemical industrial goods factory and the brick garbage from a coax factory, respectively. Press soil S was the press soil from a sanitary pottery factory. Industrial waste of Cabinet Order No. 13 T was the heavy metal treatment waste from a waste treatment facility. Two types of sea sediments (U: A rank of environmental quality standards, COD 5 2 mg l 1; V: C rank, COD 5 8 mg l 1), which were also disposed at the final reclaimed site, were also analyzed as a reference sample. 2.4. Analysis of chemical substances The analytical method for identification and quantification of chemical substances in industrial wastes could not be found. Then we analyzed by the method of Aceves et al. (1988) and the monitoring method for sediment by Ministry of the Environment (2001), which were used for the identification and quantification of several kinds of chemical substances in sediment. Fig. 1 shows the procedure. Fifty grams of sample was placed in a 300 ml glass bottle with cork and chemical substances were extracted with the acetone–n-hexane (1:1) mixed solution. The extracts were separated into the acid–neutral mixed fraction and fraction 4 (for basic compounds). The acid–neutral mixed fraction was further separated into fraction 1 (for aliphatic compounds), fraction 2 (for aromatic compounds) and fraction 3 (for polar compounds) by Sep-pak column chromatography (upper: alumina; lower: silica gel). Each fraction was concentrated to 2 ml and analyzed by GC–FPD (using P and S filters), GC–FTD and GC/MS. The blank test using 50 ml of purified water was also performed. Gas chromatography and GC/MS conditions were shown in Table 2. GC column was HP Ultra-2, which was commonly used as a column for environmental analysis. The range of column temperature was so wide that many kinds of chemical substances might be measured. Identification of chemical substances was performed using standard reagent or GC/MS library search. Quantification was performed for the chemical substance whose standard reagent was obtained. Naphthalene-d8 and phenanthrene-d10 were used as an internal standard reagent. Each calibration curve showed good linearity in the quantification range. The recoveries by the method were 70–120%. Ignition loss (IL) was measured by the method of sediment survey (Japan Society on Water Pollution Research, 1982). pH, COD, TOC, T-N and total phosphorus (T-P) were measured by the method of Japanese

Fig. 1. Analytical method of chemical substances in industrial wastes.

Industrial Standard K0102 (Japan Industrial Standards Committee, 1995). 2.5. Analysis of humic acids Humic acids were measured by the method of Otsuki (1978). Twenty to seventy grams of sample was placed in a 300 ml glass bottle with cork and humic acids were extracted with 200 ml of 0.1 N NaOH solution for 6 h. The extract solution was centrifuged at 3000 rpm and the supernatant was filtrated through a Whatman GF/B glass microfibre filter and a 0.45 lm membrane filter, in turn. By adding HCl, humic acids were precipitated from the filtrate at 51 of pH. Humic acids were gathered by filtration with the Whatman GF/B glass microfibre filter, which had previously been weighed after washing with the same solutions. The humic acids residue was washed with 0.1 N HCl solution, purified water, the ethyl alcohol–benzene (1:1)

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Table 2 GC and GC/MS conditions

Column Column temperature Injector temperature Detector temperature Detector Carrier gas Transfer line temperature Mode

GC

GC/MS

HP Ultra-2 0.35 mm · 25 m · 0.52 lm 40 C (3 min)–10 C min 1–300 C (20 min) 300 C 300 C FID, FPD, FTD N2 50 ml min 1 – –

HP Ultra-2 0.35 mm · 25 m · 0.52 lm 40 C (3 min)–10 C min 1–300 C (20 min) 230 C – MS He 260 C Split less Purge after 3 min

mixed solution and ethyl ether, in turn. The washed humic acids residue was air-dried and weighed. 2.6. Elution test The elution tests for the industrial wastes, which contained many kinds of chemical substances, were performed. The elution tests for slag J, inorganic wastes, and sea sediment V were also performed as references. Sample was placed in a 500 ml stainless steel bottle with cork so as to be 3 w/v% of solid matter and the bottle was made up to 500 ml with purified water, pH 4 (HCl) solution or pH 10 (NaOH) solution. The bottle was shaken for 6 h (Japan Environment Agency, 1994) and the eluate was filtrated through a 1 lm glass microfibre filter. As for sea sediment, the elution test using seawater was also performed. Five hundreds milliliters of filtrate were used for analysis of chemical substances referring to the method previously described. pH, COD (or TOC), T-N and T-P were also measured. 2.7. Pyrolysis Pyrolysis was performed referring to the method of Yamamoto et al. (1986). Three milligrams of sample

Fig. 2. Pyrolyzer.

powdered after 2 h drying at 105 C was placed in a sample boat and was pyrolyzed using the pyrolyzer shown in Fig. 2. Pyrogram of sample was obtained using GC–FID. Sample was decomposed at 800 C of nitrogen atmosphere for 20 s. The sample boat was pulled after heating and stood for 2 min at the injection port. Identification of each peak was performed by GC/MS analysis of the hexane solution which absorbed decomposition products. Gas chromatography and GC/MS conditions were same as shown in Table 2.

3. Results and discussion 3.1. Identification and quantification of chemical substances by GC/MS Table 3 shows the quantified chemical substances. Alkanes, benzenes, polyaromatic hydrocarbons (PAHs), phenols, furans, phthalates, thiophenes, benthiocarb, quinolines, chlordenes and nonachlors were detected in the concentration range from 1.1 to 890 ng g 1. Alcohols, steroids, ketones, benzoquinones, sulfur, nitrile compounds, amino compounds, amido compounds, pyridines, isoquinolines, carbazoles and acridines were also detected. The concentration levels of alkanes, PAHs and phtalates were higher than those of the other kinds of chemical substances. However, those levels in the industrial wastes were lower than in sea sediment V. In sludge D from the treatment for water supply, PAHs, steroids, alcohols, ketones and benthiocarb, which existed in the source of water supply, were detected. In cinder G, coronene, phenols and benzoquinones, which were the incineration products, were detected. In dust H, thiophenes, nitrile compounds, acridines, chlordenes and nonachlors except for benzenes, PAHs, steroids, phenols, ketones and furans were detected. Phenols, aminoanisoles, steroids and perylene and steroids were detected in cast sand O, garbage of glass and pottery Q, press soil S and industrial waste of Cabinet Order No. 13 T, respectively. In garbage of brick R, benzenes, PAHs, phenols, ketones, furans,

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Table 3 Identified chemical substances in industrial wastes Industrial waste

Chemical substance

Concentration (ng g 1)a

Sludge B

n-C13H28 n-C14H30 n-C15H32 n-C16H34 n-C17H36 Di-2-ethylhexyl phthalate

580 ± 180 820 ± 110 890 ± 92 800 ± 120 470 ± 74 560 ± 68

n-C17H36 n-C18H38 n-C19H40

30 ± 12 25 ± 11 27 ± 13

n-C20H42 n-C21H44 n-C22H46 n-C23H48 n-C24H50 n-C25H52 n-C26H54 n-C27H56 1,3-Dimethylnaphthalene 2,6-Dimethylnaphthalene Benzo[a]pyrene Di-n-butyl phthalate Di-n-heptyl phthalate Di-2-ethylhexyl phthalate Benthiocarb

20 ± 9 36 ± 16 20 ± 10 21 ± 6 26 ± 18 24 ± 12 18 ± 6 16 ± 7 6.8 ± 1.4 3.2 ± 0.6 5.8 ± 0.6 30 ± 10 25 ± 5 22 ± 12 4.2 ± 1.1

Coronene n-C28H58 Ethylbenzene o-Xylene m-Xylene p-Xylene Isopropylbenzene Naphthalene 1-Methylnaphthalene 2-Methylnaphthalene 1,3-Dimethylnaphthalene 2,6-Dimethylnaphthalene Acenaphthylene Anthracene or phenanthrene Fluoranthene Benzo[a]anthracene Benzo[ghi]fluoranthene Pyrene Chrysene or triphenylene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene Benzo[ghi]perylene Coronene Dibenzofuran Xanthene Di-n-butyl phthalate

18 ± 8 14 ± 3 43 ± 12 67 ± 18 8.4 ± 3.6 54 ± 15 8.1 ± 3.2 230 ± 56 65 ± 12 98 ± 23 130 ± 32 110 ± 42 70 ± 33 370 ± 58 400 ± 62 260 ± 89 200 ± 88 410 ± 96 220 ± 76 230 ± 95 250 ± 34 360 ± 92 95 ± 34 190 ± 58 72 ± 24 160 ± 46

Sludge D (water supply)

Cinder G Dust H

Industrial waste

Cast sand O

Garbage Q (glass and pottery) Garbage R (brick)

Press soil S

Chemical substance

Concentration (ng g 1)a

cis-Nonachlor trans-Nonachlor n-C22H46 n-C23H48 n-C27H56 Phenol

1.1 ± 0.5 1.6 ± 0.3 6.5 ± 1.0 6.8 ± 0.8 7.2 ± 0.6 7.1 ± 0.5

Di-n-butyl phthalate n-C12H26 Diaminoanisole

8.9 ± 1.2 5.3 ± 0.6 2.1 ± 0.4

n-C11H24 n-C12H26 n-C13H28 n-C14H30 n-C15H32 n-C16H34 n-C17H36 n-C18H38 n-C19H40 n-C20H42 n-C21H44 n-C22H46 n-C23H48 n-C24H50 Methylbenzene

68 ± 16 140 ± 40 150 ± 66 170 ± 70 180 ± 66 120 ± 54 140 ± 76 150 ± 64 150 ± 85 170 ± 52 180 ± 62 170 ± 74 180 ± 35 190 ± 67 71 ± 12

o-Xylene 110 ± 58 m-Xylene 11 ± 5 p-Xylene 67 ± 25 Isopropylbenzene 12 ± 4 Naphthalene 46 ± 9 1-Methylnaphthalene 85 ± 22 2-Methylnaphthalene 190 ± 53 1,3-Dimethylnaphthalene 230 ± 62 2,6-Dimethylnaphthalene 210 ± 82 Benzo[b]fluorene 210 ± 82 Anthracene or phenanthrene 360 ± 89 Fluoranthene 450 ± 98 Benzo[b]fluoranthene 320 ± 63 Chrysene or triphenylene 350 ± 79 Naphthacene 280 ± 58 Pyrene 410 ± 71 Benzo[a]pyrene 340 ± 83 Indeno[1,2,3-cd]pyrene 210 ± 95 Pentacene 190 ± 45 Perylene 360 ± 94 Benzo[ghi]perylene 230 ± 52 Dibenzofuran 210 ± 45 Di-n-butyl phthalate 230 ± 85 Quinoline 15 ± 7 Benzo[f]quinoline 1.8 ± 0.7 Di-2-ethylhexyl phthalate 150 ± 63 (continued on next page)

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Table 3 (continued) Industrial waste

Chemical substance

Concentration (ng g 1)a

Industrial waste

Chemical substance

Concentration (ng g 1)a

Di-2-ethylhexyl phthalate Dibenzothiophene cis-Chlordane trans-Chlordane

250 ± 73 190 ± 58 1.5 ± 0.7 1.6 ± 0.4

Industrial waste of Cabinet Order No. 13 T

Perylene Di-2-ethylhexyl phthalate

560 ± 130 380 ± 93

These compounds were detected but not quantified: C3–5-naphthaleneD,H,R C4-azuleneR C1–2-fluoreneR C1–4-anthracene or phenanthreneD,H,R Benzoanthracene or benzophenanthreneH,R C1–2-benzoanthracene or benzophenanthreneR C-chrysene or triphenyleneR Benzochrysene or benzotriphenyleneR C1–2-pyreneH,R BenzoacephenanthryleneR C-benzoacephenanthryleneR C2-tetrahydronaphthaleneR C-octahydronaphthaleneH C12-tetradecahydrophenanthreneD C10-phenolG C-tetrahydronaphthalenolR C2-octahydronaphthalenolH OctahydrophenanthrenolH SteroidsD,HST PhenalenoneH,R Benzoanthracenone or benzophenanthrenoneR C8-cyclohexadienedionD C8-benzoquinoneG Anthracenedione or phenanthrenedioneH C1–4-dihydronaphthalenoneR CyclopentaphenanthrenoneH C-dibenzofuranR BenzonaphthofuranH,R C-dibenzothiopheneR BenzonaphthothiopheneR C1–2-benzonaphthothiopheneR DinaphthothiopheneR BenzobisbenzothiopheneR S8D,H,R FluoranthenamineR FluoranthenamidoR Naphthalene carbonitrileH DiphenylpyridineR AcenaphthopyridineR C3-quinolineR IndenoquinolineR PhenylisoquinolineR IndenoisoquinolineR C2 3-carbazoleR BenzocarbazoleR C-acridineR BenzoacridineH,R C1–2-benzoacridineR. Mean ± SD (n = 3). a The weight is based on dry weight. D Sludge D. G Cinder G. H Dust H. R Garbage R. S Press soil S. T Industrial waste of Cabinet Order No. 13 T.

thiophenes, amino compounds, amido compounds, pyridines, quinolines, isoquinolines, carbazoles and acridines were detected. Garbage R contains the residues of incineration. Most types of industrial wastes contained alkanes and phthalates. The total ion monitoring (TIM) chromatograms of 3 sludges from the treatment for water supply produced very similar peak patterns. The TIM chromatograms among the other 3 sludges, among 5 slags and between 2 cast sands did not produce similar peak patterns. There were many unidentified peaks on the TIM chromatograms of sludge D, dust H and garbage R. Then, we estimated the number of each kind of chemical substance in these wastes using GC/MS library search, GC–FPD (using P and S filters) and GC–FTD. Fig. 3 shows the numbers of chemical substances detected in sludge D, dust H and garbage R. The ratios of aliphatic compounds and steroids, aromatic compounds and steroids and aromatic compounds were relatively higher than those of the other kinds of chemical substances in sludge D, dust H and garbage R, respectively. The ratios of C,H-compounds, O-compounds, S-compounds, Ncompounds and X-compounds were 49–56%, 28–40%, 2–6%, 4–19% and 1–5%, respectively. The ratios of Ncompounds in garbage R and X-compounds in dust H were higher. 3.2. Amount of humic acids Humic acids are formed from land and marine plants and may be present in water supply sludge, sewage

sludge and sediment. Humic acids have hydrophobic part and hydrophilic part such as –COOH, –OH, –NH2, –CO–, etc. in molecule. These parts are related to the elution behaviors of chemical substances (Yamamoto et al., 1981; Kim et al., 1999) and metals (Oka et al., 1981). In some river and sea sediments, humic acids are contained at near 40% of IL value and COD value of humic acids dominates at over 20% of total COD value (Ishikawa et al., 1994). In this investigation, only 0.004–0.320% of humic acids were detected in IL of sludge C, D, F and dust H as shown in Table 1. The humic acids in sludge D or F are considered to originate in environmental water. Their origins in sludge C and dust H are unknown. 3.3. Elution of chemical substances For sludge B, sludge D, dust H and garbage R, which contained many chemical substances, the elution behaviors of chemical substances were studied. The elution tests for slag J and sea sediment V were also performed as references. The buffering capacity of the 3 solutions used in the elution test was low. As a result, three solutions in each sample had the same pH after shaking. The 3 solutions in each sample also showed the nearly same COD (or TOC), T-N and T-P values after 6 h shaking. Table 4 shows the elution behavior of each item with purified water. Sludge D was produced by the treatment for water supply in neutral condition and sea sediment V had kept pH balance with seawater. The pH values of the eluates were near neutral. On the other hand, sludge

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Fig. 3. Number of detected chemical substances: (a,b) using a GC/MS; (c) using GC–FPD and GC–FTD.

B was produced by the coagulation sedimentation of heavy metals and dust H and slag J contain alkaline materials. Their eluates were in alkaline range. COD values ranged from 1.9 to 27.5 mg l 1 (or TOC 2.2 to 14.3 mg l 1) and were not necessarily proportioned with each IL value. In case of sludge B and D, metallic hydroxides caused by coagulation sedimentation were contained in IL and the elution of organic compounds was also reduced by the effect of coagulation. The IL of garbage R contains the residues of incineration. In case of sea sediment, COD, T-N and T-P values of eluate with purified water were higher than

those of eluate with seawater by 3.8, 1.7 and 6.9, respectively, as shown in Table 4. The difference in the elution behaviors of chemical substances was also observed same as in those of these items. Table 5 shows the concentrations of chemical substances in eluate. Though sludge D and sea sediment V contained relatively more chemical substances, only a little of chemical substances were eluted from these samples. C13–17-alkanes, which were main chemical substances, were eluted from sludge B. The concentration level was higher than those of sludge D, dust H, garbage R and sea sediment V. However the level was below 50 lg l 1.

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Table 4 Water quality of eluate in the elution test of industrial wastes Industrial waste

IL (%)

Humic acids (mg g 1)a

pH

COD (mg l 1)

T-N (mg l 1)

T-P (mg l 1)

Sludge Sludge (water supply) Dust Slag Garbage (brick)

B D H J R

27.5 ± 3.1 45.2 ± 8.3 50.0 ± 3.9 1.8 ± 0.2 58.0 ± 10.2

0.00 ± 0.00 0.89 ± 0.10 1.60 ± 0.46 – 0.00 ± 0.00

11.6 ± 0.1 6.6 ± 0.0 9.6 ± 0.1 12.2 ± 0.0 8.3 ± 0.0

27.5 ± 0.5 2.2 ± 0.5b 14.3 ± 0.8b 7.6 ± 0.3 6.0 ± 0.5b

0.60 ± 0.10 6.90 ± 0.43 2.40 ± 0.35 13.1 ± 0.72 1.35 ± 0.33

<0.05 <0.05 0.45 ± 0.08 <0.05 <0.05

Sea sediment

V

20.5 ± 2.3

3.51 ± 1.05

8.2 ± 0.0

12.2 ± 0.6

1.46 ± 0.15

4.92 ± 0.51

7.6 ± 0.0

3.2 ± 0.4

0.88 ± 0.11

0.71 ± 0.05

c

Seawater

Mean ± SD (n = 3). a The weight is based on dry weight. b TOC value. c pH: 8.0 ± 0.0; COD: 1.6 ± 0.3 mg l 1; T-N: 0.17 ± 0.02 mg l 1; T-P: <0.05 mg l 1.

3.4. Pyrolysis products The industrial wastes except for slag, cast sand and garbage of metal, whose IL values were low, were pyrolyzed under nitrogen atmosphere. Fig. 4 shows their pyro-

Table 5 Concentrations of chemical substances in eluate Industrial waste

Chemical substance

Concentration (lg l 1)

Sludge

B n-C13H28 n-C14H30 n-C15H32 n-C16H34 n-C17H36 Di-2-ethylhexyl phthalate

Sludge (water supply)

D Di-n-butyl phthalate 0.5 ± 0.2 Di-n-heptyl phthalate 0.4 ± 0.1 Di-2-ethylhexyl phthalate 0.4 ± 0.1

Dust

H Ethylbenzene o-Xylene p-Xylene Di-n-butyl phthalate Di-2-ethylhexyl phthalate

Garbage (brick)

R n-C11H24 n-C12H26 n-C13H28 n-C14H30 n-C15H32 n-C16H34 n-C17H36 n-C18H38 n-C19H40 Methylbenzene o-Xylene p-Xylene Di-n-butyl phthalate

Mean ± SD (n = 3).

22.2 ± 12.3 30.3 ± 9.1 35.5 ± 8.3 30.4 ± 10.1 18.8 ± 7.6 24.7 ± 14.8

0.7 ± 0.3 1.2 ± 0.5 0.9 ± 0.3 7.9 ± 2.9 10.7 ± 3.5 2.8 ± 0.6 4.7 ± 0.9 4.8 ± 1.1 5.0 ± 1.4 5.2 ± 1.3 4.3 ± 1.2 4.5 ± 0.7 4.2 ± 1.1 3.9 ± 1.4 1.7 ± 0.4 1.8 ± 0.7 1.0 ± 0.4 8.3 ± 1.9

grams. Though the peak pattern of pyrogram varied, many common pyrolysis products were observed. Amount of the pyrolysis products of sludge A, cinder G, garbage Q, press soil S, industrial waste of Cabinet Order No. 13 T and sea sediment U were low. Fig. 5 shows the TIM chromatograms of pyrolysis products of sludge D, dust H and garbage R that produced much pyrolysis compounds. Yamamoto et al. (1986) identified about 130 of alkanes, alkenes, isoprenoydo hydrocarbons, aliphatic acid methyl esters, aliphatic acids, alkyl benzenes, indenes, naphthalenes, phenols, furans, cyclopentenones, pyrols, pyridines and indoles by the pyrolysis of kelogen of lake sediment. They said that these compounds were produced by the pyrolyses of lipid, carbohydrate, amino acids, protein and lignin. The organic matter of sludge D is composed of the organic matter in environmental water. Accordingly, it is considered for sludge D that: aliphatic compounds were produced from lipid; C2benzenes were from lipid, amino acids and protein (Shulman and Simmonds, 1968); C4,8-benzenes were from carotynoid (Achari et al., 1973; Van de Meent et al., 1980); phenols were from amino acids, protein (Simmonds et al., 1969) and lignin (Bracewell and Robertson, 1976; Bracewell et al., 1980); furans were from carbohydrate (Simmonds et al., 1969); cyclopentenones were from humic acids (Wilson et al., 1983); pyrols, pyridines and benzonitryls were from amino acids (Simmonds et al., 1969; Bracewell and Robertson, 1984) and protein (Simmonds et al., 1969; Bracewell and Robertson, 1984; Yamamoto et al., 1986). Polyaromatic hydrocarbons, which were detected in dust H and garbage R, are considered to originate in incineration product. In this experiment, the pyrolyses were performed under nitrogen atmosphere to examine the characteristic of organic component. However, it could be considered that the same organic substances are also produced by the incineration of some wastes because the same organic

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Fig. 4. GC–FID pyrograms of industrial wastes.

substances were often produced in atmospheric condition, too (Yasuhara, 1991).

4. Conclusions Chemical substances in 11 different types of industrial wastes were identified. Alkanes and phthalates were detected in most types of industrial wastes. Many kinds of aromatic, cyclic aromatic, O-, S- and N-compounds were detected in the incineration wastes. Moreover, there is a possibility that these compounds increase by

the pyrolysis or incineration of the organic materials contained in wastes. The chemical substances detected in waste at the highest concentration were alkanes, PAHs and phtalates. The elution concentrations of these chemical substances were below 50 lg l 1. However the elution at higher concentration of the other water-soluble chemical substances, which can not be detected by GC/MS method, is considered. Though the outline of chemical substances in several types of industrial wastes was grasped by this study, chemical substances in industrial wastes and their behaviors are different by a category of industry, materials and

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Fig. 5. TIM chromatograms of pyrolysis products of industrial wastes: 1–3,5 C2-benzene; 4 C2(@)-benzene; 6 methyl-2cyclopentenone; 7 C2-pyrrole; 8,10 C2-pyridine; 9 C2(@)-pyridine; 11 benzaldehyde; 12,13,15,17 C3-benzene; 14 hydroxybenzenesulfonic acid; 16 Cl2-benzene; 18,19 C3(@)-benzene; 20 C3(„)-benzene; 21,25 C-phenol; 22 C2(„)-benzene methanol; 23,26,28,32 C4-benzene; 24 Cl-phenylethanone; 27 tetrahydronaphthalene; 29,35 C-benzonitrile; 30,34,37,43,45,46,50 C2-phenol; 31 C-benzofuran; 33,36,38,39,41,44 C4(@)-benzene; 40,42 C-indene; 47,51,54–58,61,63,65 C3-phenol; 48 naphthalene; 49 azulene; 52 C2-benzofuran; 53 dihydroxytetrahydronaphthalene; 59,60,62,64,66 C-dihydronaphthalene; 67 C2-indene; 68,73,75 C4-phenol; 69 dihydroindenone; 70 benzene acetonitrile; 71,72 C-naphthalene; 74 dihydroindenol; 76 C2(@)-naphthalene; 77 C-indole; 78–82,84 C2-naphthalene; 83 biphenylene; 85 C6-benzene; 86 C-biphenyl; 87 naphthalene carbonitrile; 88,90–93,95,97 C3-naphthalene; 89 dibenzofuran; 94 tetrahydrofluorene; 96 fluorene; 98,99 C2-biphenyl; 100,101 C-dibenzofuran; 102,104 C5-naphthalene; 103 C-fluorene; 105,106 anthracene or phenanthrene; 107 fluoranthene; 108 pyrene.

production process even if the industrial wastes were legally same type. Moreover, mixing of other wastes and uneven quality of sample are also considered (Tasaki and Urano, 2000). Therefore, it is necessary to grasp their production and sending-in processes in order to manage the chemical substances in industrial wastes appropriately.

Acknowledgments We are grateful to Dr. Osami Nakasugi for his advice and the Japan Society of Waste Management Experts supported this work.

References Aceves, M., Grimalt, J., Albaige´s, J., 1988. Analysis of hydrocarbons in aquatic sediments II: evaluation of com-

mon preparative procedures for petroleum and chlorinated hydrocarbons. J. Chromatogr. 436, 503–509. Achari, R.G., Shaw, G., Holleyhead, R., 1973. Identification of ionene and other carotenoid degradation products from the pyrolysis of sporopollenins derived from some pollen exines, aspore coal and the Green River shale. Chem. Geol. 12, 229–234. Aoi, K., Ono, Y., Namiki, K., Yamada, A., 2002. Environmental impact evaluation of heavy metals contained in the fly and bottom ash. Waste Manage. Res. 13 (3), 124– 130. Bracewell, J.M., Robertson, G.W., 1976. A pyrolysis-gas chromatography method for discrimination of soil humus type. J. Soil Sci. 27, 196–205. Bracewell, J.M., Robertson, G.W., 1984. Quantitative comparison of the nitrogen-containing pyrolysis products and amino acid composition of soil humic acids. J. Anal. Appl. Pyrolysis 6, 19–29. Bracewell, J.M., Robertson, G.W., Welch, D.I., 1980. Polycarboxylic acids as the origin of some pyrolysis products characteristic of soil organic matter. J. Anal. Appl. Pyrolysis 2, 239–248.

S. Ishikawa et al. / Chemosphere 59 (2005) 1343–1353 Bramlett, J., Furman, C., Johnson, A., Ellis, W.D., Nelson, H., Vick, W.H., 1987. Composition of leachates from actual hazardous waste sites. PB87-1987 43, p. 113. Brown, M.A., Kim, I.S., Roechl, R., Sasinos, F.I., Stephens, R.D., 1989. Analysis of target and nontarget pollutants in aqueous leachates from the hazardous waste site Stringfellow, California, via ion chromatography-particle beam and inductively coupled plasma mass spectrometry. Chemosphere 19, 1921–1927. Coleman, W.E., Melton, R.G., Kopfler, F.C., Barone, K.A., Aurand, T.A., Jellison, M.G., 1980. Identification of organic compounds in a mutagenic of a surface drinking water by a computerized gas chromatography mass spectrometry system (GC/MS/COM). Environ. Sci. Technol. 14, 576–588. Francis, C.W., White, G.H., 1987. Leaching of toxic metals from incinerator ashes. J. Water Pollut. Control Fed. 59, 979–986. Ishikawa, S., Uchimura, Y., Ueda, N., Kido, K., 1994. Distribution of humic acids in sea and estuary sediments in Kitakyushu-city and their contribution to organic pollution. J. Resour. Environ. 30, 231–237. Japan Environment Agency, 1994. Environmental Decree and Explanation. Gyosei, Tokyo, pp. 2037–2050. Japan Industrial Standards Committee, 1995. JIS Handbook: Measurement of Environment-1995. Japanese Standards Association, Tokyo, pp. 973–1188. Japan Society on Water Pollution Research, 1982. Guideline for Lake Environmental Survey: Methods for Sediment Survey. Technical Environmental Pollution Control, Tokyo, p. 151. Kim, Y.J., Ohsako, M., Lee, D.H., 1999. A study on the solubility of PCDDs/DFs when in coexistence with dissolved humic matter. Waste Manage. Res. 10 (4), 214–223. Lema, J.M., Mendezor, R., Blazquez, R., 1988. Characteristics of landfill leachates and alternatives for their treatment. A Review. Water Air Soil Pollut. 40, 223–250. Ministry of the Environment, 2001. Chemicals in the Environment. Ministry of the Environment, Tokyo, p. 155. Nakasugi, O., 1993. Pollution and control of groundwater for volatile organic chlorine compounds. Kyushu Branch Seminar-1992. Japan Society on Water Environment, pp. 6–15. Oka, H., Hunaki, M., Itoh, J., 1981. Adsorption of mercury (II) chloride on sulfonated peat humic acid. Jpn. J. Water Pollut. Res. 4, 163–169.

1353

Otsuki, T., 1978. Studies on the humic acid in shallow-sea sediments. J. Environ. Pollut. Control 14, 309–315. Reinhard, M., Goodman, N.L., Barker, J.F., 1984. Occurrence and distribution of organic chemicals in two landfill leachate plumes. Environ. Sci. Technol. 18, 953–961. Sakai, S., Ogawa, M., Takatsuki, H., 1991. Hazardous materials in shredder wastes and their appropriate treatment system. Waste Manage. Res. 2 (2), 33–42. Shulman, G.P., Simmonds, P.G., 1968. Thermal decomposition of aromatic and heteroaromatic amino acids. Chem. Commun., 1040–1042. Simmonds, P.G., Shulman, G.P., Stembridge, C.H., 1969. Organic analysis by gas chromatograph–mass spectroscopy: a candidate experiment for the biological exploration of mars. J. Chromatogr. Sci. 7, 36–41. Tasaki, T., Urano, K., 2000. Statistical analysis of variability of test data by sampling methods of multicomposition wastes. Waste Manage. Res. 11 (5), 280–289. US EPA, 1993. Innovative technology. Annual Status Report EPA 542-R-93-003. Van de Meent, D., Brown, S.C., Philip, R.P., Simoneit, B.R.T., 1980. Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography–mass spectrometry of kerogens and kerogen precursors. Geochim. Cosmochim. Acta 44, 999–1013. Wilson, M.A., Philp, R.P., Gillan, A.H., Gilbert, T.D., Tate, K.R., 1983. Comparison of structures of humic substances from aquatic and terrestrial sources by pyrolysis gas chromatography–mass spectrometry. Geochim. Cosmochim. Acta 47, 497–502. Yamamoto, S., Ishiwatari, R., Honnami, H., 1981. Possible interaction of insoluble organic geopolymers (kerogen) with alkylbenzenesulfonates. Jpn. J. Water Pollut. Res. 4, 65–72. Yamamoto, S., Ishiwatari, R., Philp, P.R., 1986. Pyrolysis/GC/ MS analysis of insoluble organic lake geopolymers (kerogen). Geochemistry 20, 39–50. Yasuhara, A., 1991. Burning/Pyrolysis and Chemical Substances. Japan Society for Environmental Chemistry, Ibaragi. Yasuhara, A., 1995. Chemical components in leachates from hazardous wastes landfills in Japan. Toxicol. Environ. Chem. 51, 113–120. Yasuhara, A., Uno, Y., Nakasugi, O., Hosomi, M., 1992. Analysis of chemical components in landfill leachate. Part 2. J. Environ. Chem. 2, 541–546.