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Production and use of DDT containing antifouling paint resulted in high DDTs residue in three paint factory sites and two shipyard sites, China Jia Xin a,, Xiang Liu a , Wei Liu a , Lu Jiang a , Jihua Wang b , Jia Niu b a Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, China b College of Life Science and Technology, Harbin Normal University, Harbin 150025, China article info Article history: Received 6 September 2010 Received in revised form 8 March 2011 Accepted 1 April 2011 Available online 7 May 2011 Keywords: Dichlorodiphenyltrichloroethanes (DDT) Environmental pollution Paint factory Shipyard abstract This study provides the first intensive investigation of Dichlorodiphenyltrichloroethanes (DDT) distribu- tion in typical paint factories and shipyards in China where DDT containing antifouling paint were mass produced and used respectively. DDTs were analyzed in soil, sludge and sediment samples collected from three major paint factories and two shipyards. The results showed that the total DDTs concentrations detected in paint factory and shipyard sites ranged from 0.06 to 8387.24 mg kg 1 . In comparison with paint factory sites, the shipyard sites were much more seriously contaminated. However, for both kinds of sites, the DDTs level was found to be largely affected by history and capacity of production and use of DDT containing antifouling paint. (DDE + DDD)/DDT ratios indicated that DDT containing antifouling paint could serve as important fresh input sources for DDTs. It can be seen that most samples in shipyards were in ranges where heavy contamination and potential ecological risk were identified. Ó 2011 Elsevier Ltd. All rights reserved. 1. Introduction Dichlorodiphenyltrichloroethanes (DDT) is a typical persistent organic pollutant (POPs) that possesses high toxicity and low degradability. It was widely used in China as a pesticide from the 1950s until the production of DDT was officially banned in 1983, which accounted for the DDTs detection in agricultural soil (Shi et al., 2005; Gao et al., 2008; Hu et al., 2009a,b) and severe DDTs contamination of pesticide plant sites (Liu et al., 2008a,b; Zhang et al., 2009a,b). Over more than 30 years, the production of DDT in China was estimated to be 0.4 million metric tons, accounting for 20% of the total world production. Recently, DDTs were detected in various environmental med- ium of coastal regions. For example, high DDTs level was detected in 58 sediment samples from nine typical fishing harbors along the coastal line of China and they were generally 1–2 orders of magni- tude higher than those of the adjacent estuarine/marine sediments (Lin et al., 2009). And the DDTs residue in a shipyard area of Hong Kong was detected to be 3.6–33.4 mg kg 1 (Chiu et al., 2006). In addition, a recent monitoring campaign of POPs in the atmosphere across Asia, using passive sampling techniques, also reported that the DDT concentrations in the atmosphere over the eastern coastal zone of China, in particular in the Pearl River Delta (PRD) of South China, were the highest in East Asia (Jaward et al., 2005). After the agricultural use of technical DDT has been prohibited, DDT is still allowed to be used for hygiene purposes, such as malaria control, in Asian developing countries, including China, upon the 5-year exemption of the Stockholm Convention. However, this seems inadequate to explain why such high concentrations of DDTs mostly occurred in the coastal regions, provided that dicofol is used both in inland and coastal regions of the country. So the use of DDT containing antifouling paint was identified to be an impor- tant source of DDTs in the coastal zone of China. Since 1950s, DDT began to serve as efficient addictives for anti- fouling paint. There were 300 000 medium and small size ships widely distributed along the 18 000 km coastline in China, which consumed 10 000 metric tons antifouling paints. Approximately half was DDT based antifouling paint, and the other half was Tribu- tyltin (TBT) based antifouling paint (SEPA GEF Project, 2008). Given to that annually, a great amount of DDT containing antifouling paint were produced and used from the paint factories (antifouling paint manufacturer) and shipyards (antifouling paint consumer), which triggered great potential risk for human health and ecosystem. However, few efforts have been made on exploring the DDT res- idues in paint factory sites and shipyard sites, and it is not known yet to what extent these sites were polluted and the exact pollu- tion distribution. The objectives of our study were to (i) determine the spatial distribution of DDTs concentrations in typical paint fac- tory and shipyard sites in China, (ii) identify the difference of DDTs among the sites and propose the major impact factors and (iii) as- sess the DDTs pollution in paint factory sites and shipyard sites in China. Specifically, we quantified DDTs in soil, sludge and sediment 0045-6535/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2011.04.005 Corresponding author. Tel.: +86 010 62797667; fax: +86 010 62785685. E-mail address: [email protected] (J. Xin). Chemosphere 84 (2011) 342–347 Contents lists available at ScienceDirect Chemosphere journal homepage: www.elsevier.com/locate/chemosphere

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Chemosphere 84 (2011) 342–347

Contents lists available at ScienceDirect

Chemosphere

journal homepage: www.elsevier .com/locate /chemosphere

Production and use of DDT containing antifouling paint resulted in high DDTsresidue in three paint factory sites and two shipyard sites, China

Jia Xin a,⇑, Xiang Liu a, Wei Liu a, Lu Jiang a, Jihua Wang b, Jia Niu b

a Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, Chinab College of Life Science and Technology, Harbin Normal University, Harbin 150025, China

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

Article history:Received 6 September 2010Received in revised form 8 March 2011Accepted 1 April 2011Available online 7 May 2011

Keywords:Dichlorodiphenyltrichloroethanes (DDT)Environmental pollutionPaint factoryShipyard

0045-6535/$ - see front matter � 2011 Elsevier Ltd. Adoi:10.1016/j.chemosphere.2011.04.005

⇑ Corresponding author. Tel.: +86 010 62797667; faE-mail address: [email protected] (J. X

This study provides the first intensive investigation of Dichlorodiphenyltrichloroethanes (DDT) distribu-tion in typical paint factories and shipyards in China where DDT containing antifouling paint were massproduced and used respectively. DDTs were analyzed in soil, sludge and sediment samples collected fromthree major paint factories and two shipyards. The results showed that the total DDTs concentrationsdetected in paint factory and shipyard sites ranged from 0.06 to 8387.24 mg kg�1. In comparison withpaint factory sites, the shipyard sites were much more seriously contaminated. However, for both kindsof sites, the DDTs level was found to be largely affected by history and capacity of production and use ofDDT containing antifouling paint. (DDE + DDD)/DDT ratios indicated that DDT containing antifoulingpaint could serve as important fresh input sources for DDTs. It can be seen that most samples in shipyardswere in ranges where heavy contamination and potential ecological risk were identified.

� 2011 Elsevier Ltd. All rights reserved.

1. Introduction

Dichlorodiphenyltrichloroethanes (DDT) is a typical persistentorganic pollutant (POPs) that possesses high toxicity and lowdegradability. It was widely used in China as a pesticide from the1950s until the production of DDT was officially banned in 1983,which accounted for the DDTs detection in agricultural soil (Shiet al., 2005; Gao et al., 2008; Hu et al., 2009a,b) and severe DDTscontamination of pesticide plant sites (Liu et al., 2008a,b; Zhanget al., 2009a,b). Over more than 30 years, the production of DDTin China was estimated to be 0.4 million metric tons, accountingfor 20% of the total world production.

Recently, DDTs were detected in various environmental med-ium of coastal regions. For example, high DDTs level was detectedin 58 sediment samples from nine typical fishing harbors along thecoastal line of China and they were generally 1–2 orders of magni-tude higher than those of the adjacent estuarine/marine sediments(Lin et al., 2009). And the DDTs residue in a shipyard area of HongKong was detected to be 3.6–33.4 mg kg�1 (Chiu et al., 2006). Inaddition, a recent monitoring campaign of POPs in the atmosphereacross Asia, using passive sampling techniques, also reported thatthe DDT concentrations in the atmosphere over the eastern coastalzone of China, in particular in the Pearl River Delta (PRD) of SouthChina, were the highest in East Asia (Jaward et al., 2005). After theagricultural use of technical DDT has been prohibited, DDT is still

ll rights reserved.

x: +86 010 62785685.in).

allowed to be used for hygiene purposes, such as malaria control,in Asian developing countries, including China, upon the 5-yearexemption of the Stockholm Convention. However, this seemsinadequate to explain why such high concentrations of DDTsmostly occurred in the coastal regions, provided that dicofol isused both in inland and coastal regions of the country. So the useof DDT containing antifouling paint was identified to be an impor-tant source of DDTs in the coastal zone of China.

Since 1950s, DDT began to serve as efficient addictives for anti-fouling paint. There were 300 000 medium and small size shipswidely distributed along the 18 000 km coastline in China, whichconsumed 10 000 metric tons antifouling paints. Approximatelyhalf was DDT based antifouling paint, and the other half was Tribu-tyltin (TBT) based antifouling paint (SEPA GEF Project, 2008). Givento that annually, a great amount of DDT containing antifoulingpaint were produced and used from the paint factories (antifoulingpaint manufacturer) and shipyards (antifouling paint consumer),which triggered great potential risk for human health andecosystem.

However, few efforts have been made on exploring the DDT res-idues in paint factory sites and shipyard sites, and it is not knownyet to what extent these sites were polluted and the exact pollu-tion distribution. The objectives of our study were to (i) determinethe spatial distribution of DDTs concentrations in typical paint fac-tory and shipyard sites in China, (ii) identify the difference of DDTsamong the sites and propose the major impact factors and (iii) as-sess the DDTs pollution in paint factory sites and shipyard sites inChina. Specifically, we quantified DDTs in soil, sludge and sediment

J. Xin et al. / Chemosphere 84 (2011) 342–347 343

samples collected in three major DDT containing antifouling paintfactories from three coastal cities in China (Qingdao, Shanghai andGuangdong) and two major shipyards which used to consume agood amount of such paint located in the city of Weihai and Yan-gjiang respectively.

2. Materials and methods

2.1. Study area and sampling

In this study, among the five target sampling sites, the threelocated in Qingdao (QD), Shanghai (SH) and Guangzhou (GZ) arepaint factories where DDT containing antifouling paint was pro-duced, while those two in Weihai (WH) and Yangjiang (YJ) areshipyards where DDT containing antifouling paint was peeled orsprayed for ships. A total of 55 samples were collected from May2010 to June 2010. For the paint factories, the sampling pointswere set to cover the wastewater sewers, the natural soil nearbythe DDT warehouse, production workshop and garden soil, whilefor the shipyards, the sampling locations were mainly at paint-peeling spots, shoreline sediment and the offshore sediment.

All in all, the sampling points were set to be tested for thepotential most serious contamination level and whether the natu-ral soil or sediment fell victim to the production and use of the DDTcontaining antifouling paint.

For most cases, surface soil (0–20 cm) and surface sediment (0–30 cm) were collected. However, for some sewers with little sludgesedimentation, the sampling depth was set at 0–5 cm. All the sam-ples collected were kept in sealed Kraft packages respectively toavoid contamination and transported to the laboratory immedi-ately. And they were maintained at 4 �C prior to chemical analysis.

2.2. Reagents

Acetone, and n-hexane obtained from Fisher Scientific Interna-tional Inc., USA were of High Performance Liquid Chromatography(HPLC) grade. Standard solutions of four DDTs including p,p0-DDT,o,p0-DDT, p,p0-DDE and p,p0-DDD were obtained from Institute forEnvironmental Reference Materials of Ministry of EnvironmentalProtection (IERM), China, at concentrations of 100 mg L�1. Dilu-tions were made in n-hexane in order to cover the entire rangeof DDTs expected in the samples. All solutions were stored at�20 �C. Pentachloronitrobenzene (PCNB), obtained from Labor Dr.Ehrenstorfer, Germany, was used as internal standard. Cleanertflorisil was purchased from Agela Technologies Co., Ltd., China.Anhydrous sodium sulfate, obtained from Beijing Chemical Fac-tory, China, was heated at 400 �C for 4 h prior to use. All glasswareswere pre-washed and rinsed with distilled solvent (acetone) beforeuse.

2.3. Extraction and cleanup

For pretreatment, the samples were first freeze-dried, pulver-ized, and sieved through 60 mesh stainless steel sieve. All soiland sediment samples were extracted by accelerated solventextraction method (ASE300, Beijing Titan Instruments Co. Ltd., Chi-na). Five grams of soil sample and 2.5 g diatomite were mixed to-gether and the diatomite was used as dispersant. One piece ofcellulose filter paper and the mixed sample described above weresequentially layered from the bottom of the ASE cell (22 mL vol-ume). The extraction was then carried out with n-hexane/acetone(1:1, V:V) at a temperature of 115 �C and a pressure of 1500 psi.The extraction was repeated three times for each sample. The com-bined extracts were evaporated to approximately 2 mL by rotaryevaporator (RE-52, Shanghai Yarong Company, China) in a water

bath at 35 �C. The concentrated extract was transferred to thetop of a prepared cleanert florisil column (1 g/6 mL). Prior to use,the cleanert florisil was successively filled with 1 cm of anhydroussodium sulfate. Then the column was eluted first by 5 mL of hex-ane. After that, the column was eluted by 10 mL of hexane/acetone(9:1, V:V) and this part of the elution was collected for DDTs deter-mination. The collected elution was concentrated by a rotary evap-orator and then blown to 2 mL under gentle nitrogen stream. Eightmicrolitres of PCNB (50 lg mL�1) as internal standard was addedto the 2 mL concentrated extract prior to GC analysis.

2.4. Chromatographic analysis

Four major isomers and metabolites of DDT in the extracts wereanalyzed with a 7890 gas chromatograph equipped with a 5975MSD. A HP-5 fused silica capillary column (30 m � 0.25 mm ID,and 0.25 m film thickness) was used, with high-purity helium ascarrier gas was at 1 mL min�1. The temperature of injector anddetector were kept at 210 and 300 �C, respectively. The tempera-ture program of column oven was set to 60 �C, kept for 5 min, thenwith 25 �C min�1 to 235 �C, kept for 2 min, and further by2 �C min�1 to 250 �C. Pulse splitless injection of a 1 lL samplewas performed with a 6 min solvent delay time. The residues ofDDTs were determined by comparing the peak areas of the samplesadjusted by internal standard and the calibration curves of thestandards.

2.5. Quality assurance and quality control

The limit of detection (LOD) for each compound, taken as threetimes the response of the signal-to-noise (S/N), was 0.1 ng g�1 forp,p0-DDE, 0.1 ng g�1 for p,p0-DDD, 0.3 ng g�1 for o,p0-DDD, and0.2 ng g�1 for p,p0-DDT. The average recoveries by this methodwith fortified samples were from 77.5% for p,p0-DDE, 88.3% forp,p0-DDD, 97.6% for o,p0-DDD and 92.5% for p,p0-DDT. The reportedconcentrations of DDTs were not corrected for surrogate recover-ies. The calibration curves of DDTs were determined before eachbatch of samples being analyzed, with the correlation coefficients(r) all greater than 0.99. All of the calibration curves were adjustedby internal standard to remove the change of instrument responsesignal caused by matrix effect and instrument instability. The ex-tent of degradation must be less than 15% before the analysis ofDDTs could proceed.

3. Results and discussion

3.1. Concentrations of DDTs

The mean concentrations, median concentrations and concen-tration ranges of each DDT compound were summarized in Table1. It showed that the total DDTs (sum of four isomers) werebetween 0.06 and 8387.24 mg kg�1. The range of p,p0-DDE wasbetween 0.008 and 203.32 mg kg�1, while the p,p0-DDD wasbetween 0.007 and 399.43 mg kg�1, the o,p0-DDT between 0.001and 1310.60 mg kg�1 and p,p0-DDT between 0.025 and 6473.88mg kg�1. However, the percentage of individual compounds indifferent samples followed different sequence.

The mean concentration of DDTs in each paint factory site andshipyard site were 20–37 242 times higher than that in urban soilsof Beijing (68.14 ng g�1) (Yang et al., 2010). Similarly, the level ofDDTs in this study was much higher than the highest detected con-centration of DDTs in Haihe Estuary, China (Zhao et al., 2010). Thissuggested that the paint factory sites and shipyard sites were seri-ously affected by anthropogenic DDT containing antifouling paintproduction and use activities.

Table 1The mean, median, and range of p,p0-DDE, p,p0-DDD, o,p0-DDT, p,p0-DDT, and

PDDTa (mg kg�1, dry weight) in the different sampling locations.

Site p,p0-DDE p,p0-DDD o,p0-DDT p,p0-DDTP

DDT

QD Mean ± SD 0.25 ± 0.38 0.23 ± 0.27 0.24 ± 0.30 0.66 ± 0.83 1.38 ± 1.32Median 0.49 0.12 0.11 0.29 1.32Range 0.008–0.90 0.007–0.66 0.001–0.73 0.025–2.05 0.04–2.82

SH Mean ± SD 0.45 ± 0.39 2.21 ± 3.38 0.74 ± 0.80 5.26 ± 7.42 8.67 ± 11.98Median 0.30 0.35 0.34 1.02 1.90Range 0.10–1.11 0.08–8.07 0.17–2.11 0.90–18.12 1.46–29.41

GZ Mean ± SD 10.39 ± 10.50 15.03 ± 21.21 6.04 ± 9.92 45.94 ± 95.36 77.40 ± 130.82Median 8.73 2.22 1.82 3.15 18.54Range 0.021–22.68 0.023–56.34 0.03–27.82 0.044–259.00 0.12–365.31

WH Mean ± SD 5.00 ± 9.56 47.06 ± 101.63 9.65 ± 19.28 45.09 ± 96.57 106.79 ± 226.82Median 0.67 4.08 0.66 1.63 6.86Range 0.46–29.87 1.90–314.30 0.38–59.19 0.89–396.48 3.71–699.84

YJ Mean ± SD 72.67 ± 79.27 143.12 ± 157.41 388.17 ± 540.82 1928.54 ± 2699.67 2532.49 ± 3488.10Median 29.42 69.42 20.28 85.75 198.80Range 6.29–203.32 4.52–399.43 3.97–1310.60 7.14–6473.88 22.38–8387.23

a PDDT represents the sum of four isomers of DDT.

0

2

4

p,p'

-DD

D/p

,p'-D

DT

0 2 4

0 2 40

2

4

(b) shipyard sites

p,p'-DDE/p,p'-DDT

p,p'

-DD

D/p

,p'-D

DT

(a) paint factory sites

Fig. 1. Comparison of p,p0-DDE/p,p0-DDT to p,p0-DDD/p,p0-DDT in paint factory sites(a) and shipyard sites (b).

344 J. Xin et al. / Chemosphere 84 (2011) 342–347

In comparison with one pesticide plant in Jiangsu Provincewhich represented another kind of potentially DDT-contaminatedsite, the mean DDTs level in QD and SH were 1 magnitude lower,and that in GZ was close, however, those in shipyards were dra-matically higher than that. It was indicated that besides pesticidefactories, paint factories and shipyards were also important poten-tial DDT contamination sites.

Hypotheses about DDT potential contamination contributionfrom its use of antifouling paint have been proposed recently (Liet al., 2007; Wang et al. 2007; Hu et al., 2009a,b; Zheng et al.,2010). From 9 typical fishing harbors, high DDTs levels (9–7350 ng g�1) coupled with the lower concentrations of hexachloro-cyclohexane (HCH) and total organic carbon (TOC) were detected(Lin et al., 2009). DDTs level in a shipyard area in Hong Kong wasup to 3.6–33.4 mg kg�1 (Chiu et al., 2006). The long-term MusselWatch program in Asia found that the mussel samples from coastalChina had the highest concentrations of DDTs in Asia (Monirithet al., 2003). Data of DDTs level in bivalves from Guangzhou bays,Bohai Sea and Yellow Sea showed that new input of DDT existedand lacquer painting on fisher boat was analyzed to be a possiblesource (Jin et al., 2008; Liu et al., 2008a,b; Gan et al., 2009; Zhanget al., 2009). And in our study, the high detected concentrations ofDDTs further indicated DDT containing antifouling paint was pos-sibly a major contamination source for the coastal regions.

3.2. Compositions of DDTs

Because DDT is reductively dechlorinated to DDD under anaer-obic conditions and to DDE under aerobic conditions (Hiter andDay, 1992), so the ratio of DDD to DDE is a good index to indicatewhether the DDT is degraded under aerobic or anaerobic condi-tions. Given to the higher p,p0-DDE and p,p0-DDD ratio detectedin the study compared to the commercial products composition,it was indicated that biodegradation as the major process forDDT attenuation under natural conditions definitely occurred inthese locations, which confirmed the applicability of the above in-dex in our study. The ratio of DDD to DDE in all samples rangedfrom 0.19 to 10.52. The ratio was higher than 1% for 79% of allthe samples, and Fig. 1 showed that 64.28% of paint factory sam-ples and 84.62% of shipyard samples had higher DDD percentageagainst DDE, which indicated that at most of the sampling sitesDDTs were degraded under anaerobic condition.

The ratio of (p,p0-DDE + p,p0-DDD) to p,p0-DDT can be used toindicate whether p,p0-DDT in soils is ‘‘aged (degraded)’’or ‘‘new (in-put recently)’’ (Qiu et al., 2004). If the ratio is higher than 1, itmeans that DDTs in soils are aged mixtures and if the ratio is lower

than 1, it indicates that the parent DDT is inputted to soils recently.In this study, the ratios of the samples ranged from 0.09 to 4.56.The ratio was higher than 1 for 50% of the samples, indicating thathalf of the sampling sites still had DDTs input recently. There wereonly 28.57% of paint factory samples whose ratio were higher than1, but the proportion for shipyard samples was up to 66.67%, whichindicated possibly after the ban of production of DDT containingantifouling paint, still some paint in stock could support furtheruse of shipyards.

3.3. Comparison of DDTs levels in paint factories (antifouling paintmanufacturer) and shipyards (antifouling paint consumer)

For three different paint factories, the mean DDTs level in eachfactory followed the sequence: GZ > SH > QD. Among all the sam-

0.01

0.1

1

10

100

1000

Lg [D

DTs

]

Garden area

Raw material warehouse

Production workshop

Fig. 3. Box plot for Lg[DDTs] in samples from garden area, raw material warehousesand production workshops in paint factory sites.

soil wastewater sewer sludge

0

20

40140

160

Con

cent

ratio

n of

DD

Ts (m

g kg

-1)

QD SH GZ

(a) paint factory sites

J. Xin et al. / Chemosphere 84 (2011) 342–347 345

ples, the very sample with highest DDTs concentration was col-lected from wastewater sewer outside raw material warehouseof GZ. In addition, among the four sampling points whose DDTs le-vel was higher than 10 mg kg�1, one came from SH, while anotherthree all from GZ. Different from QD and SH, GZ failed to relocateduring its whole production history, so its long production historyand large production capacity could possibly account for its highercontamination level.

For the two shipyards, in terms of average DDTs concentration,YJ overwhelmed WH dramatically. The highest DDTs level detectedin YJ was up to 8387.23 mg kg�1, while its counterpart in WH wasonly 699.84 mg kg�1. The difference could probably be attributedto the longer history for paint spraying and peeling and absenceof an efficient waste disposal system in YJ.

From Fig. 2, the DDTs concentrations (the lowest, the mean andthe highest values) of paint factories were lower than those of theshipyards. For the paint factories, they took relatively severe pro-tective measures in case that some potential accidental leakageshould happen during storage, transportation and mixing. So inthis way the potential risk had been greatly lowered and thechance for DDT exposure had been effectively reduced. Neverthe-less, for the shipyards, the paint was in situ peeled and sprayed,after what the DDT containing wastes were in situ piled withoutany further disposal. In addition, the workers preferred to washtheir tools on the shore, then where a large amount of DDT wouldbe accumulated.

3.4. Spatial distribution in paint factory sites and shipyard sites

As indicated in Fig. 3, the most seriously contaminated area forpaint factories were located nearby the production workshop andthe raw material warehouse, where DDTs level were one or twomagnitude higher than that of garden area.

In addition, as shown in Fig. 4a, both for raw material ware-house and production workshop, the high DDTs level tended tobe detected in inner and outer wastewater sewer sludge, whilethe natural soil nearby contained relatively lower DDTs level com-pared to the sludge, although they did also suffered from mild DDTcontamination. The workshop and warehouse cleaning would pos-sibly make the accidental leaked DDT powder and DDT containingpaint residues flow into and accumulate in the wastewater sewers,while for the natural soil environment, it was normally less possi-ble to be exposed to the DDT pollution, let alone under severesupervision during DDT transportation from warehouse to produc-tion workshop, which could account for DDTs accumulation prefer-ence to sewers.

For the shipyards, as shown in Fig. 4b, the most seriously con-taminated points were located in the paint-peeling and spraying

0.01

0.1

1

10

100

1000

10000

Lg [D

DTs

]

Paint factory sites Shipyard sites

Fig. 2. Box plot for Lg [DDTs] in paint factory sites and shipyard sites.

sites and the shoreline sediment. Firstly, the workers peeled offthe paint from the ship body on site, yet rarely cleaned them up.So a large amount of DDT remained here, accounting for the highDDTs level in the paint peeling and spraying sites. Secondly, theworkers used to clean their tools on the shore or dump the wastepaint to inshore seawater. That’s why high level DDTs were de-tected in the paint-peeling and spraying sites and the shorelinesediment. In addition, with rise and fall of the tides, some contam-inants flowed with the currents and precipitated at the offshore

paint-peeling spot soil

0

200

400

600

800

6000

8000

Con

cent

ratio

n of

DD

Ts (m

g kg

-1)

WHYJ

(b) shipyard sites

shorelinesediment

off-shoresediment

Fig. 4. DDTs distribution in different sampling areas in paint factory sites (a) and inshipyards sites (b).

346 J. Xin et al. / Chemosphere 84 (2011) 342–347

area. That was why low level DDTs were also detected in offshoresediment.

3.5. Pollution and ecological risk assessment

In China, the Chinese Environmental Quality Standard for Soils(GB 15618-1995), which is categorized into three grades, is usuallyused to assess the soil quality. And the maximum allowable con-centration for DDTs of grade III is 1 mg kg�1, representing theworst soil quality. Among other foreign countries, the Netherlandscould really stand out in terms of the contaminated-site remedia-tion achievement. Their soil and groundwater quality standards arerisk-based, so their soil remediation intervention value could moretruly reflect its potential risk to humans and ecosystem. And itsintervention value for DDTs is 4 mg kg�1.

For the samples collected from paint factories, 28.57% containedhigh DDTs levels which exceeded 4 mg kg�1 and 35.71% containedDDTs levels which were between 1 mg kg�1 and 4 mg kg�1, whileanother 35.72% contained DDTs which were lower than 1 mg kg�1.Therefore, the samples highly, moderately and rarely contami-nated respectively accounted for similar proportion.

For the samples collected from shipyards, those samples whoseDDTs concentration were higher than 4 mg kg�1 accounted for92.86% of the total, with another 7.14% between 1 mg kg�1 and4 mg kg�1. So most of the samples in shipyards could be regardedas heavy contamination.

For ecological risk estimation, the DDT soil quality criteria cal-culated based on secondary poisoning of top predators by a prob-abilistic model were adopted. It showed that the derivedmaximum permissible concentration of DDT in the soil for birds,mammals, and soil organisms were 0.011, 0.19, and 0.01 mg kg�1

respectively (Jongbloed et al., 1996). Given to that, the DDTs levelin natural soil where ecological exposure would possibly occur inGZ and both shipyard sites were above the threshold, which indi-cated that there did exist huge ecological risk, while no significantecological risk was observed in QD and SH. In addition, to evaluatethe ecotoxicological aspect of marine sediment contamination, thelevels of the contaminants in the two shipyard sites where sedi-ment samples were analyzed were compared with the EffectsRange-Low (ERL) and Effects Range-Median (ERM) values referredin US-EPA/National Oceanic and Atmospheric Administration(NOAA) sediment quality guidelines (SQGs) for marine sediments(Long et al., 1995). The ERL and ERM values are intended to definechemical concentration ranges that are rarely, occasionally, or fre-quently associated with adverse biological effects. Both shipyardssites in the study near the marine environment exceeded theERM (46.1 ng g�1). This indicated that the DDTs contaminatedshipyard sites seriously posed adverse biological effects to thenearby marine environment.

4. Conclusions

DDT and its metabolites were detected in the three paint factorysites and two shipyard sites. The total DDTs concentrations variedfrom 0.06 to 8387.24 mg kg�1, which suggested these sites wereseriously affected by anthropogenic DDT containing antifoulingpaint production and use activities. Analysis of the source of DDTscontamination suggested a freshly input source. The DDT metabo-lites were dominated by DDD, which revealed for most of the sam-ples DDT was preferentially degraded to DDD under anaerobiccondition. Among the three paint factory sites, there were signifi-cant positive correlation between DDTs level and production his-tory and capacity. For the two shipyard sites, the usage historyand management system contributed to the difference of theirDDTs level. In comparison with paint factory sites, the shipyard

sites were much more seriously contaminated. Spatial distributionanalysis revealed that DDTs contamination in shipyards centeredaround paint-peeling sites and the shoreline sediments. For thepaint factories, DDT contamination was mainly caused by cleaningthe workshop and leakage during transportation. According to Chi-nese Environmental Quality Standard for Soils (GB 15618-1995)and the Netherland soil remediation intervention value, both ship-yard sites could be defined as heavy contamination, while for thethree paint factory sites, heavy contamination of DDTs just oc-curred in several samples, especially from GZ. Based on some pub-lished soil and sediment quality criteria, significant ecological riskwas identified in GZ and both shipyard sites, therefore, detailedrisk assessment and management should be introduced to protectworkers there from the direct exposure.

Acknowledgements

The study was supported by Alternatives to DDT Usage in theProduction of Antifouling Paint project of United Nations Develop-ment Program (3664/CHN10/00043092).

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