Chemosphere 85 (2011) 1719–1724

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Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Andrea Colombo ⇑, Emilio Benfenati, Simona Grazia Bugatti, Giorgio Celeste, Marco Lodi,Giuseppe Rotella, Vincenzo Senese, Roberto FanelliDepartment of Environmental Health Sciences, Istituto di Ricerche Farmacologiche ‘‘Mario Negri’’, Via La Masa 19, 20156 Milano, Italy

a r t i c l e i n f o a b s t r a c t

Article history:Received 27 January 2011Received in revised form 5 August 2011Accepted 22 September 2011Available online 20 October 2011

Keywords:DioxinFuransSoilsALSPCA

0045-6535/$ - see front matter � 2011 Elsevier Ltd. Adoi:10.1016/j.chemosphere.2011.09.018

⇑ Corresponding author. Tel.: +39 02390514536; faE-mail address: andrea.colombo@marionegri.it (A.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in sam-ples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. Thepurpose was to estimate the impact of the emissions on the surrounding environment.

PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted inItaly in soils for green areas and residential uses and the upper limit of several reference concentrations.The most contaminated sites were less than 500 m from the plant and the dioxin concentration with thedistance from the ALS.

Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/Fcontamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore usefulto identify sources of emission causing contamination.

� 2011 Elsevier Ltd. All rights reserved.

1. Introduction

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlori-nated dibenzo-p-furans (PCDFs) are persistent organic pollutants(POPs) of great concern because of their high toxicity and tendencyto bioaccumulate through the food chain. One of the aims of theStockholm convention, adopted in 2001, is to protect humansand the environment against POPs, reducing in particular the unin-tentional release of PCDD/Fs. Human exposure has been associatedwith damage to the liver and immune system, adverse reproduc-tive effects and cancer (Birnbaum, 1995; De Vito and Birnbaum,1995; ATSDR, 1997; Haws et al., 2006; Schecter et al., 2006). Manycountries have now compiled inventories of dioxin sources to bet-ter understand and quantify the amounts of PCDD/Fs emitted(UNEP, 1999, 2001; Fiedler, 2007).

Secondary aluminum smelters (ALSs), for the recovery of alumi-num from used scrap and dross, may lead to the formation of PCDD/Fs (Chen et al., 2004; Li et al., 2007) probably due to the combina-tion of impurities such as plastics, paints, and solvents in the rawmaterials used in the process (Aittola et al., 1996). PCDD/Fs are re-leased into the environment and accumulate for years in environ-mental sinks such as soils and sediments, with a long half life(Sinkkonen and Paasivirta, 2000). Many studies have investigatedlevels and sources of PCDD/Fs in these of environmental samples(Czuczwa et al., 1985; Czuczwa and Hites, 1986; Hagenmaieret al., 1986; Creaser et al., 1989; Broman et al., 1991; Gotz et al.,

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x: +39 0239014735.Colombo).

1993; Rotard et al., 1994; Fiedler et al., 1996; Sakurai et al., 1996,1998; Ogura et al., 2001; Caserini et al., 2004).

The aim of the study was evaluate its impact (of the ALS) to thesurrounding environment in Piedmont (a region in the North-westof Italy). The area investigated is for crop production, especiallyrice, which is an important social and economic resource. Thusthe quality of the environment may have repercussions on humanhealth and on the local economy.

We collected ALS emission samples (chimney emissions, fly ashfrom the chimney, particulates on the surface and wastes as mate-rial for the plant) and agricultural soil samples and compared the‘‘fingerprints’’ of the PCDD/F homolog profiles of samples analyzedusing principal component analysis (PCA) also to distinguish thecontribution of the local ALS from other potential PCDD/F emissionsources. This multivariate technique is widely used to seek similar-ities between samples with a large number of variables and toidentify the origin of PCDD/F contamination in environmental sam-ples (Norwood et al., 1989; Eitzer, 1993; Tysklind et al., 1993;Wenning et al., 1993, 1994; Fattore et al., 1997, 2003; Colomboet al., 2009).

2. Material and methods

This study investigated four types of samples (three from chim-ney emissions, three from fly ashes from the chimney, seven fromparticulate on the surface of the plant and 37 from wastes asmaterial for the plant) from the secondary ALS. Stack gas sampleswere collected, using an automatic isokinetic sampling systemcomprising a filter (silica glass microfiber thimble, Whatman),

1720 A. Colombo et al. / Chemosphere 85 (2011) 1719–1724

followed by a condensing system and adsorbing trap containing re-sin (Amberlite XAD-2). The resin was spiked with 13C12-labeledsurrogate standards before sampling (Colombo et al., 2009). Thefly ash samples were collected from bag the filter, the particulatesamples from the surface of the plant and the waste samples fromthe storage areas inside the plant. The samples collected from theALS were extracted with organic solvents (toluene and hexane) in aSoxhlet apparatus and separated from interfering components in amultistage separation process which included a purification stepby an Extralut column (70-230 mesh; Merck; Darmsadt, Germany)loaded with concentrated sulfuric acid (98%), and further purifica-tion on neutral alumina columns (Merck) activated at 400 �Cbefore use (Fattore et al., 1997, 2003; Colombo et al., 2009).

Environmental samples were collected at the locations indi-cated in Fig. 1. Sampling sites were chosen on the basis of a poten-tial contamination from the plant several directions for somekilometers around, taking account of the main wind direction(from NNW to SSE). Surface composite soil samples (0–30 cm)from rice paddies were collected from 19 locations, removinglitter/grass layer, if present. USEPA Method 1613B (USEPA, 1994)was used for soil sample analysis.

The 2,3,7,8-chlorine-substituted congeners and the homologs ofeach chlorination class were detected by a TRACE GC 2000, ThermoFinnigan (Thermo Fisher Scientific), coupled with a Mat 95 XP MassSpectrometer, operating in the electron impact ionization (EI+)mode, at 10000 resolution power. A BPX-DXN (60 m � 0.20 mm �0.25 lm) (SGE, Analytical Science, Melbourne, Australia) capillary

Fig. 1. Map of the area investigated showing the soil samplin

column with splitless injection was used. The temperature pro-gram was: 160 �C for 1 min, 2.5 �C min�1 increase until 300 �C,300 �C maintained for 6 min. The monitored ions were M+ andM + 2 for tetra-CDD/Fs and M + 2 and M + 4 for penta-, hexa-, hep-ta- and octa-CDDs/Fs. Peaks were accepted if the isotopic ratio waswithin 15% of the internal standard (IS) ratio. Limit of detections(LOD) were calculate individually for each sample on the basis ofa signal-to-noise ratio of 3:1. Filed and analytical blanks, coveringthe whole sampling and analytical procedure, were run. Blanksamples showed no peaks.

Concentrations were also expressed using the most recent toxicequivalent factors (TEFs) re-evaluated by the World Health Organi-zation (WHO05-TEQ) (Van den Berg et al., 2006). For the TEQcalculations, concentrations below the LOD were considered as halfthe limit (middle bound method).

PCDD/F homologs of the obtained in the present study were or-ganized into a matrix having 100 objects (samples) and 10 variables(PCDD/F homolog values), normalized to the total concentration ofPCDD/F by expressing each homolog value as a percentage of thesum of the total PCDD/F before PCA. The Simca – P 8.0 package(Umetrics AB, Umea, Sweden) was used for the analysis.

3. Results and discussion

PCDD/F concentrations from stack gas samples were between0.01 and 0.03 ng WHO05-TEQ Nm�3 and comparable with those

g locations and the secondary aluminum smelter (ALS).

Fig. 2. Mean TEQ of PCDD/Fs in fly ash from the chimney (n = 3), particulate on thesurface (n = 7) and waste samples as material for the plant (n = 37) from asecondary aluminum smelter.

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Fig. 3. Average PCDD/Fs homolog patterns of ALS emission. The percentageindicates the contribution of the different homologs to the total of the PCDD/Fs.

A. Colombo et al. / Chemosphere 85 (2011) 1719–1724 1721

reported previously for three different aluminum plants (Chenet al., 2004; Ba et al., 2009; Wang et al., 2009).

Fig. 2 shows the mean TEQ of PCDD/Fs in the solid emissionsamples. They range from 0.59 to 1.31 ng WHO05-TEQ g�1, 0.31to 4.12 ng WHO05-TEQ g�1 and 0.002 to 0.93 ng WHO05-TEQ g�1

respectively for fly ashes, particulates and wastes. The ratio ofTEQ of PCDF to PCDD (RPCDF/PCDD) in fly ash and particulate sampleswas around 71:29 and 77:23 respectively, indicating a major con-tribution of furans. These values are comparable with those ob-tained in a previous study for these matrices (Ba et al., 2009), butvery different from values from other thermal processes, such asincineration of municipal solid wastes and wood combustion(Anderson and Fisher, 2002; Yu et al., 2006). A RPCDF/PCDD valuemuch higher than 1 indicates that de novo synthesis may be themain mechanism in dioxin formation (Anderson and Fisher,2002; Everaert and Baeyens, 2002).

The homolog distribution shown in Fig. 3 gives a better view ofPCDD/Fs from the ALS. Stack gas and waste sample mean profilesare very similar, showing tetrachlorinated (TCDF) and pentachlori-nated furans (PeCDF) as dominants, while in particulate and fly ashsamples hexachlorinated furans and dioxins contribute morealthough TCDF and PeCDF remain the major contributors to thetotal PCDD/F concentration.

Table 1 presents the PCDD/F soil concentrations (pg g�1). Thesevalues range from 0.20 to 64.0 pg WHO05-TEQ g�1 (23–3104 pg g�1 as

PPCDD/Fs). Soils sampled closest to the plant, A,

B, C and D, exceed the limit of 10 pg WHO-TEQ g�1 adopted in Italyin soils for green and residential uses (Ministry for Environmentand Territory and Sea, 2006), while none exceed the thresholdfor commercial and industrial soils (100 pg WHO-TEQ g�1) (Minis-try for Environment and Territory and Sea, 2006). In Europe there isno directive that establishes PCDD/Fs values in soils in relation totheir possible uses, although in Germany a limit of 5 pg I-TEQ g�1

was set to permit the use of soils for agricultural purposes (BUNR,1992).

The upper limit of the results was higher than the typical valuesand ranges obtained in other sites in Italy. For instance elsewherein Piedmont (the region of the present investigation) the mean val-ues for agricultural and natural soils are respectively 1.34 and2.99 pg WHO-TEQ g�1 (ARPA, 2004). In Reggio Emilia provincethe range for unpolluted soils is between 1.9 pg I-TEQ g�1 and

2.4 pg I-TEQ g�1 (Capuano et al., 2005), while in Northern Italy,in the proximity of municipal solid waste incinerators, valuesrange between 0.08 pg I-TEQ g�1 and 1.5 pg I-TEQ g�1 (Caseriniet al., 2004).

Many studies have measured PCDD/Fs emission sources, and as-sessed their impact on the environment so as to identify the originof contamination (Deister and Pommer, 1991; Jimenez et al., 1996;Schuhmacher et al., 1997, 1999, 2000, 2002; Domingo et al., 2000,2001; Caserini et al., 2004; Park et al., 2004; Colombo et al., 2009).One method is levels of PCDD/Fs with the distance from a certainsite. In general if dioxin concentrations tend to decrease at longerdistances, then the site can be considered a source of PCDD/Fs (Ohet al., 2006).

Fig. 4 shows the PCDD/F concentrations in soils at different dis-tances from the ALS: there is a decrease at increased distances.PCDD/Fs were highest close to the secondary ALS, less than500 m from the plant, ranging from pg 5 to 64 pg WHO05-TEQ g�1;at longer distances the soil concentrations were between 0.90 and2.7 pg WHO05-TEQ g�1, falling to values in the range for rural soilsin Piedmont (ARPA, 2004). Furthermore, higher levels were foundin locations downwind (SSE), while the lowest value (0.20 pgWHO05-TEQ g�1) was in the sample taken 8 km away, whichserved as our background soil.

On the basis of these considerations Fig. 5 reports the meanhomolog profiles of soils grouped according to the distance fromthe ALS. The differences in patterns were mainly due to a highercontent of PCDDF than PCDD in soils collected at less than500 m, although octachlorodibenzo-p-dioxin (OCDD) is dominant.From this distance outwards the content of PCDDF tends to drop,but the fingerprint remains different from that of the backgroundsample.

Higher levels of furans indicate the presence of potential com-bustion sources of PCDD/Fs (Fiedler et al., 1996; Oh et al., 2006)and comparing the PCDD/F fingerprints of different sources withthe patterns obtained in environmental samples it is possible indi-cates the origin of the contamination (Fattore et al., 1997, 2003;Colombo et al., 2009). We therefore did a PCA to see whether theALS was responsible for PCDD/F levels in soil. The method allowsthe investigation of the original data matrix using the smallestnumber of variables while preserving the greatest possible amountof information (Colombo et al., 2009). Data from municipal solidwaste incinerator (MSWI) (Colombo et al., 2009), steel plant(Colombo et al., 2009), emissions from the ALS, and soil sampleswere used. Each homolog concentration was normalized on thetotal PCDD/F in order to avoid the weight due to differences in

Table 1PCDD/F concentrations (pg g�1) in soil samples collected around the secondary aluminum smelter.

Sample A B C D E F G H I J K L M N O P Q R BKGLocation 45�2505500N 45�2505400N 45�2601200N 45�2505000N 45�2505000N 45�25049’’N 45�2505300N 45�2503800N 45�2502900N 45�2500600N 45�2403000N 45�2602800y 45�2404600N 45�2505500N 45�2403000N 45�26033’’N 45�2802200N 45�26028’’N 45�2201100N

8�13’2000E 8�13’20’E 8�13’1900E 8�13’2000E 8�13’4500E 8�13’4500E 8�13’4200E 8�13’4700E 8�14’2800E 8�13’1500E 8�13’1500E 8 = 14’5100E 8�14’0300E 8�12’1700E 8�13’1500E 8 = 16’0400E 8�13’2200E 8�14’1200E 8�17’2600EConcentration Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1 Pg g�1

2,3,7,8-ICDD 2.47 1.60 0.60 0.72 0.53 0.53 0.29 0.28 0.14 0.37 0.13 0.18 0.26 <0.02 0.07 0.09 0.04 <0.01 <0.011,2,3,7,8-PeCDD 8.71 6.25 1.43 1.57 1.28 0.95 0.66 0.75 0.34 0.26 0.44 0.20 0.23 0.20 0.25 <0.03 0.07 0.07 0.031,3,4,7,8-HiCDD 10.81 6.57 1.50 1.19 1.26 0.92 0.45 0.72 0.30 0.31 0.44 0.15 0.16 0.32 0.19 0.25 0.19 0.04 0.041,2,3,7,8-H1CDD 18.34 13.46 3.08 2.68 2.29 2.44 1.09 1.68 0.95 1.07 1.23 0.46 0.53 1.19 0.70 0.56 0.31 0.16 0.111,2,3,7,8,9-HxCDD 12.42 7.33 2.03 2.15 1.79 1.71 0.65 1.07 0.55 0.71 0.55 0.37 0.41 0.76 0.47 0.34 0.33 0.09 0.131,2,3,4,6,7,8,-

HpCDD85.33 49.46 20.49 20.24 19.62 36.32 7.93 11.65 7.25 18,58 13.28 7.46 6.50 20.56 5.52 4.61 2.89 1.68 1.43

OCDD 124.96 80.32 79.41 64.76 66.19 145.21 28.11 79.37 34.61 127.19 80.40 35.95 47.01 108.59 34.55 28.51 14.44 12.60 7.802.3.7.8-ICDF 75.26 62.51 15.06 15.21 12.09 13.42 5.93 7.07 2.91 2.90 1.95 1.76 1.82 0.90 1.33 1.60 1.10 0.37 0.141,2,3,7,8-PeCDF 35.35 28.96 6.52 5.29 4.23 4.01 2.53 3.09 1.59 1.42 1.89 0.56 0.79 0.44 0.75 0.83 0.42 0.23 0.062,3,4,7,8-PeCDF 70.19 48.69 11.13 9.77 7.89 7.23 4.52 5.61 2.45 1.81 1.85 1.13 1.33 1.16 1.07 1.04 0.77 0.36 0.171,2,3,4,7,8-HiCDF 42.38 28.67 6.53 5.71 5.61 4.55 2.35 3.53 2.25 1.59 2.16 0.93 1.16 1.22 1.17 1.07 1.16 0.26 0.161,2,3,6,7,8-EhCDF 44.79 30.26 7.09 5.49 5.24 4.35 2.17 3.27 1.54 1.47 1.53 0.55 0.59 0.55 0.52 0.56 0.64 0.21 0.102,3,4,6,7,8-HiCDF 58.90 38.94 7.85 6.96 6.19 5.52 2.59 4.47 2.36 1.76 1.95 3.84 1.22 0.97 1.02 1.11 0.90 0.31 0.151,2,7,8,9-HICDF 19.22 10.92 2.19 2.05 1.60 1.96 0.25 1.32 0.75 0.51 0.73 1.34 0.34 0.23 0.32 0.05 0.07 0.07 0.041,2,3,4,6.7.8-HpCDF 138.69 91.18 20.13 19.65 20.14 16.55 7.04 10.36 9.23 6.87 9.07 3.72 4.32 11.65 5.30 4.65 4.69 1.12 0.771,2,3,4,7,8,9,HpCDF 22.34 12.28 2.55 2.33 2.67 2.31 0.96 1.26 1.04 0.74 1.40 0.47 0.56 1.29 0.54 0.62 0.42 0.11 0.06OCDF 112.89 73.31 22.57 22.02 21.22 15.81 10.21 11.34 11.51 9.64 17.27 4.52 7.13 52.75 7.85 6.66 8.34 1.56 4.13WH005-TEQ 64.05 44.76 10.57 10.07 5.36 7.89 4.11 5.38 2.6y 2.55 2.53 1.54 1.71 1.60 1.43 1.13 0.90 0.35 0.20RTCDD 105.98 64.65 28.71 28.66 14.68 8.58 5.51 7.06 4.05 5.11 4.89 1.99 2.16 2.94 2.47 1.97 1.35 0.32 0.15RPeCDD 200.12 140.07 38.53 38.40 24.69 17.45 13.88 10.29 7.37 6.59 6.64 3.65 4.52 4.53 4.89 2.55 2.60 0.79 0.34RHxCDD 338.82 213.30 49.58 53.52 36.84 33.52 20.02 25.46 11.97 13.26 14.72 6.54 7.09 10.38 5.23 7.11 4.64 1.72 1.18RHpCDD 180.72 104.03 42.09 40.45 37.97 62.29 16.25 24.30 14.75 34.72 25.65 13.91 13.29 33.11 16.14 5.41 5.36 3.51 2.41OCDD 124.96 80.32 79.41 64.76 66.19 145.21 28.11 79.37 34.61 127.19 80.40 35.95 47.01 108.59 34.55 28.51 14.44 12.60 7.80RTCDF 777.13 550.11 161.65 160.62 120.25 101.40 53.27 57.06 32.63 24.76 25.61 13.27 14.63 25.44 20.64 18.24 10.98 1.53 2.14RPeCDF 643.22 450.81 131.77 115.31 89.00 84.32 47.48 32.47 24.42 19.51 20.10 12.72 11.89 17.33 12.14 9.45 10.24 4.31 2.12RHxCDF 415.16 280.96 60.56 53.51 50.57 41.73 23.25 33.76 18.84 14.26 17.95 8.06 9.49 20.93 9.72 9.67 7.70 1.45 1.75RHpCDF 205.46 120.87 28.64 26.15 30.45 24.62 10.39 15.13 11.91 9.65 16.06 5.72 6.46 32.11 5.15 7.11 6.47 1.60 0.87ROCDF 112.89 73.31 22.57 22.02 21.22 15.81 10.21 11.34 11.51 9.64 17.27 4.52 7.13 52.75 7.85 6.66 5.34 1.56 4.15RPCDDs 950.60 602.37 238.32 225.78 180.36 267.05 83.77 146.48 72.77 187.17 132.30 62.04 74.07 159.85 66.27 48.87 28.92 18.93 11.88RPCDFs 2153.86 1476.07 405.18 377.61 311.49 267.37 144.60 149.75 99.32 77.85 96.99 44.29 49.61 148.56 58.51 51.14 43.73 10.75 11.06

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Fig. 4. PCDD/Fs concentrations in soils at different distances from the plant.

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Fig. 5. Average PCDD/Fs homolog patterns of soil samples grouped according to thedistance from the ALS. The percentage indicates the contribution of the differenthomologs to the total of the PCDD/Fs.

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Fig. 6. Principal component analysis (PCA) score plot on the PCDD/F homologgroups of soil samples collected less than 500 m from the ALS (D), >500 m from theALS (s), background soil (h) and samples related to known emission sources:cluster A includes secondary aluminum smelter samples (�); cluster B includesmunicipal solid waste incinerator (MSWI) samples (d) and cluster C includes steelplant samples (j).

A. Colombo et al. / Chemosphere 85 (2011) 1719–1724 1723

concentrations. Fig. 6 gives the PCA score plot, with the samplesanalysed shown in the space of the first and second component.The first component takes into account 40% of the variability ofthe dataset, and was mainly influenced by lower-chlorinatedPCDD/Fs in a negative direction; consequently samples in whichthese homologs are dominant are on the left, while samples witha higher content of high chlorinated PCDD/Fs are on the right.The second component accounts for 28% of the variability of thedata set and is mainly influenced by PCDD in the positive directionand PCDF in negative direction. Thus, the second component dis-tinguish samples on the basis of their PCDD/PCDF ratio, i.e. sampleswith higher PCDDs are on the upper part of the figure, while sam-ples with higher PCDFs in the lower part of the figure.

The samples related to emission form three clusters: cluster Aincludes samples from the ALS (�); cluster B includes samples ofemissions from the MSWI (d) and the third, cluster C, includessamples from steel plant (j). There are three outliers from clusterA in both components, whose fingerprint is different from the aver-age pattern of ALS emissions. Soils sampled closest to the plant (D)almost all fall in the first cluster; the remaining data are spread outon the right side of the figure and are farther from ALS cluster asthe proportion of higher chlorinated homologs increases, in partic-ular as OCDD contribution raises.

In conclusion assessing the distance of soil samples from theALS and using a multivariate analysis technique like PCA identifiedwith certainty the PCDD/F emission source responsible for soil con-tamination in the area investigated. This analysis clearly showedthat PCDD/F soil levels taken less than 500 m from the ALS weremainly influenced by the emission from the plant.

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