a n a l y t i c a c h i m i c a a c t a 6 0 6 ( 2 0 0 8 ) [135][136][137][138][139][140][141][142][143][144][145][146][147][148][149][150] a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / a c a ReviewBiomonitoring: An appealing tool for assessment of metal pollution in the aquatic ecosystem

Very few studies have investigated the heavy metal contents in rice samples from a typical E-waste recycling area. In this study, 10 heavy metals (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni and Pb) in 13 polished rice and relevant hull samples, six relevant paddy soil samples were investigated. The geometric mean concentrations of Cd, Cu and Hg in soil samples were 1.19, 9.98 and 0.32 lg g À1 , respectively, which were 4.0, 2.0 and 1.1-folds of the maximum allowable concentration (MAC) (0.30, 50.00, 0.30 lg g À1 , respectively) for Chinese agricultural soils. The analyzed metal concentrations were significantly different between rice and relevant hull except for As, Cd and Hg (p < 0.05). All metal concentrations, except for Co, in rice hull were higher than those in polished rice. The geometric mean of Pb in polished rice reached 0.69 lg g À1 , which was 3.5-folds higher than the MAC (0.20 lg g À1 ) by the safety criteria for milled rice. Cd contents in 31% of the rice samples exceeded the national MAC (0.20 lg g À1 ), and the arithmetic mean also slightly exceeded national MAC. In addition, Cd and Pb contents in local rice were much higher than commercial rice samples examined in this work and previous studies. Comparing the tolerable daily intakes given by FAO/WHO with the mean estimated daily intakes; Pb daily intake through rice consumption in this area was 3.7 lg day À1 kg À1 body weight (bw), which already exceeded the FAO tolerable daily intake, and the Cd daily intake (0.7 lg day À1 kg À1 bw) through rice had already taken up 70% of the total tolerable daily intake (1 lg day À1 kg À1 bw). The daily intake of Hg and As through rice was much lower than the tolerable daily intakes, but bioaccumulation of Hg through the food chain and intake of As from other food stuff should also be of concern.

As an emerging class of environmentally persistent and bioaccumulative contaminants, perfluorinated compounds (PFCs), especially perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), have been ubiquitously found in the environment. Increasing evidence shows that the accumulated levels of PFCs in animals and the human body might cause potential impairment to their health. In the present study, toxicological effects of PFOA and PFOS on male Sprague-Dawley rats were examined after 28 days of subchronic exposure. Abnormal behavior and sharp weight loss were observed in the high-dose PFOS group. Marked hepatomegaly, renal hypertrophy, and orchioncus in treated groups were in accordance with the viscera-somatic indexes of the liver, kidney, and gonad. Histopathological observation showed that relatively serious damage occurred in the liver and lung, mainly including hepatocytic hypertrophy and cytoplasmic vacuolation in the livers and congestion and thickened epithelial walls in the lungs. PFOA concentrations in main target organs were in the order of kidney > liver > lung > (heart, whole blood) > testicle > (spleen, brain), whereas the bioaccumulation order for PFOS was liver > heart > kidney > (whole blood) > lung > (testicle, spleen, brain). The highest concentration of PFOA detected in the kidney exposed to 5 mg/kg/day was 228+/-37 microg/g and PFOS in the liver exposed to 20 mg/kg/day reached the highest level of 648+/-17 microg/g, indicating that the liver, lung, and kidney might serve as the main target organs for PFCs. Furthermore, a dose-dependent accumulation of PFOS in various tissues was found. The accumulation levels of PFOS were universally higher than PFOA, which might explain the relative high toxicity of PFOS. The definite toxicity and high accumulation of the tested PFCs might pose a great threat to biota and human beings due to their widespread application in various fields.

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Human scalp hair samples can be used to indicate environmental and occupational exposure of heavy metals due to intensive electronic waste recycling activities. a r t i c l e i n f o a b s t r a c tScalp hair samples were collected at an electronic waste (e-waste) recycling area and analyzed for trace elements and heavy metals. Elevated levels were found for Cu and Pb with geometric means (GMs) at 39.8 and 49.5 mg/g, and the levels of all elements were found in the rank order Pb > Cu [ Mn > Ba > Cr > Ni > Cd > As > V. Besides Cu and Pb, Cd (GM: 0.518 mg/g) was also found to be significantly higher compared to that in hair samples from control areas. Differences with age, gender, residence status and villages could be distinguished for most of the elements. The high levels of Cd, Cu and Pb were likely found to be originated from e-waste related activities, and specific sources were discussed. This study shows that human scalp hair could be a useful biomarker to assess the extent of heavy metal exposure to workers and residents in areas with intensive e-waste recycling activities.

A brominated flame retardant (BFR), hexabrominated heterocyclic tris-(2,3-dibromopropyl) isocyanurate (TBC), was identified, for the first time, in the natural environment. The chemical was found in river water (2.33-163 ng/L), surface sediments (85.0 ng/g-6.03 µg/g dry weight (dw)), soils (19.6-672 ng/g dw), earthworm (9.75-78.8 ng/g dw), and carp samples (12.0-646 ng/g dw) from a factory-polluted area in southern China. It was found that TBC can strongly adsorb to organic material in sediment, and a trend of decreasing concentration with distance from the source in soil and earthworm samples, combined with calculated K ow (octanol-water partition coefficient) and K oa (octanol-air partition coefficient), suggests its potential ability to undergo regional transportation through dust deposition. Calculated results showed high K ow (log K ow ) 7.37) and bioaccumulation factor (BAF) (log BAF ) 4.30) of this BFR and indicate that TBC has semivolatile properties and bioaccumulation characteristic in certain biological species. Quantitative structure property relationships (QSPRs) modeling revealed that TBC has K oa (log K oa ) 23.68) and K aw (air-water partition coefficient) (log K aw ) -16.31) values several orders higher than those of other BFRs. The identification of this chemical additive further reminds us that the production and usage of heterocyclic BFRs may cause potential contamination to the surrounding environment.

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs) and has been frequently detected in the environment and biota. Recent studies have found that derivatives of TBBPA, such as TBBPA bis(allyl) ether (TBBPA BAE) and TBBPA bis(2,3-dibromopropyl) ether (TBBPA BDBPE) are present in various environmental compartments. In this work, using liquid chromatography coupled with tandem mass spectrometry (LC−MS/MS) and liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC−Q-TOF-MS), TBBPA allyl ether (TBBPA AE) and TBBPA 2,3-dibromopropyl ether (TBBPA DBPE) were identified in environmental samples and further confirmed by synthesized standards. Soil, sediment, rice hull, and earthworm samples collected near a BFR manufacturing plant were found to contain these two compounds. In sediments, the concentrations of TBBPA AE and TBBPA DBPE ranged from 1.0 to 346.6 ng/g of dry weight (dw) and from 0.7 to 292.7 ng/g of dw, respectively. TBBPA AE and TBBPA DBPE in earthworm and rice hull samples were similar to soil samples, which ranged from below the method limit of detection (LOD, <0.002 ng/g of dw) to 0.064 ng/g of dw and from below the LOD (<0.008 ng/g of dw) to 0.58 ng/g of dw, respectively. Furthermore, mollusks collected from the Chinese Bohai Sea were used as a bioindicator to investigate the occurrence and distribution of these compounds in the coastal environment. The detection frequencies of TBBPA AE and TBBPA DBPE were 41 and 32%, respectively, and the concentrations ranged from below LOD (<0.003 ng/g of dw) to 0.54 ng/g of dw, with an average of 0.09 ng/g of dw, for TBBPA AE, and from below LOD (<0.008 ng/g of dw) to 1.41 ng/g of dw, with an average of 0.15 ng/g of dw, for TBBPA DBPE.

As an extremely complex group of persistent organic pollutants (POPs) candidates in the Stockholm Convention, short chain chlorinated paraffins (SCCPs) have been of extensive concern in recent years. In this study, nine bivalve and two gastropod species were collected in 2009 to evaluate the spatial distributions and potential factors influencing the bioaccumulation of SCCPs in mollusks in the Chinese Bohai Sea. The concentrations of ∑ SCCPs in the mollusks were in the range 64.9− 5510 ng/g (dry weight) with an average chlorine content of 61.1%. C 10 and C 11 were the predominant homologue groups of SCCPs, which accounted for about 29.7% and 34.9% of ∑ SCCPs, respectively. Six and seven chlorinated substituents were the main congener groups. Mya arenaria (Mya), Mactra veneriformis (Mac), and Crassostrea talienwhanensis (Oyster, Ost) had higher average concentrations of SCCPs than other species, implying that these bivalves could be used as sentinels to indicate SCCPs contamination in this coastal region. A significant positive linear relationship was found between SCCP concentrations and lipid content of the mollusks, whereas the lipidnormalized SCCP concentrations were negatively linear-related to the trophic levels (TL), which implied that SCCPs did not show biomagnification in mollusks in this region.