[Spatial Distribution, Speciation, and Ecological Risk Assessment of Heavy Metals in Surface Sediments of Dongjiang Lake, Hunan Province].

To understand the heavy metal pollution status of Dongjiang Lake, the contents and species of heavy metals in the surface sediments were investigated during September 2021, and the heavy metal pollution level and potential ecological risk were evaluated. The results showed that Cd, Pb, As, Cu, Zn, Ni, and Cr contents were in the range of 0.40-34.1, 14.8-1688, 6.99-1155, 6.89-280, 26.2-1739, 6.29-55.4, and 23.3-44.8 mg·kg-1, respectively, with extremely uneven spatial distributions. The highest contents of Cd, Pb, As, Zn, Cu, and Ni were found in the site adjacent to Yaogangxian tungsten ore. The proportion of metal species with bioavailability was high, in which Cd in acid-soluble species was 46.7%-71.5% and Pb in reducible species was 46.8%-67.0%. The bioavailable species of Cu, Zn, Ni, and Cr were 35%-68%, 42%-72%, 26%-51%, and 6%-30%, respectively, although they primarily existed in residual species. According to the geo-accumulation index (Igeo), there was a moderate or extreme pollution status of Cd in all sites, moderate or extreme pollution status of Pb in 90% of sites, and moderate pollution status of As, Cu, and Zn in 30% of sites. The ecological risk factor (Eri) of Cd showed high potential ecological risk in all sites with significantly high potential ecological risk in 80% of sites. Moreover, As and Pb had significantly high potential ecological risk, and Cu had moderate potential ecological risk in S7, which was adjacent to Yaogangxian tungsten ore. There was a high total potential ecological risk in all sites and significantly high potential ecological risk in 50% of sites. Therefore, the surface sediments of Dongjiang Lake were under the combined pollution of Cd, Pb, As, Zn, and Cu with high bioavailability and high total potential ecological risk.

Root Uptake Pathways and Cell Wall Accumulation Mechanisms of Organophosphate Esters in Wheat (Triticum aestivum L.).

The behavior of organophosphate esters (OPEs) in plants has drawn considerable attention because of their adverse effects to biota. However, the root uptake pathways and cell wall accumulation mechanisms of OPEs in plants are still unclear. In this study, the uptake pathways, subcellular distribution, and accumulation mechanisms of OPEs in wheat roots were elucidated. The results demonstrated that the symplast is the major pathway for uptake of both tris(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPHP) in wheat roots. Inhibitor experiments showed that the transmembrane transport of OPEs is a passive uptake process, and aquaporins and carrier proteins contribute to the uptake of OPEs. More than 69% of TCEP was accumulated in cell sap due to its high hydrophilicity, while the hydrophobic TPHP was mainly stored in the root cell wall. The sorption affinity of TPHP decreased gradually following the sequential fractionation of wheat roots, which confirmed the significant contribution to TPHP sorption on wheat roots. A significant positive correlation between the sorption affinity values and the percentage of aromatic carbon was observed (r2 = 0.856, p < 0.01), indicating that the accumulation of hydrophobic OPEs in roots does not just depend on lipids alone, but the aromatic moieties of lignin in the cell wall also contribute to OPE accumulation.

TiO2 nanoparticles enhanced bioaccumulation and toxic performance of PAHs via trophic transfer.

Engineering nanoparticles (NPs) could act as accumulator and carrier of co-contaminants, affecting their fate and toxicity in environments. However, the effects of NPs on the bioaccumulation and trophic transfer of co-contaminants through the food chain and the ensuing effects on higher predators are unclear. In the present study, we investigated the effects of titanium dioxide nanoparticles (nTiO2) on the trophic transfer of phenanthrene (Phe) from prey Artemia salina to predator Scophthalmus maximus. We also evaluated the ensuing toxic performance of Phe in S. maximus after been transferred from A. salina in the presence and absence of nTiO2. The presence of nTiO2 significantly (p < 0.05) increased Phe accumulation in A. salina with higher bioconcentration factor (BCF) up to 90.9 than that of 38.6 in Phe exposure along. After trophic transfer, nTiO2 (1 mg/L) also promoted the bioaccumulation of Phe (1 µg/L) in predator S. maximus from 4.17 mg/kg to 7.85 mg/kg (dry weight). However, nTiO2 did not enhance the trophic transfer of Phe from A. salina to S. maximus since the biological magnification factor (BMF) decreased from 0.13 to 0.08. Nevertheless, the nTiO2-enhanced bioaccumulation of Phe did enhance Phe toxicity performance in predator S. maximus after trophic transfer, showing significant (p < 0.05) growth inhibition and changes of nutrient status in the predator, compared to those of the control. Further physio-biochemical investigations suggested that oxidative stress and inhibition of digestive functions might explain the growth inhibition in treatment with nTiO2 + Phe. This study demonstrates the first evidence that NP-enhanced bioaccumulation and toxic performance of co-existing pollutants across trophic transfer, which poses potential risks to marine ecosystems, and ultimately human health by seafood consumption.

Single and joint oxidative stress of cadmium and phenanthrene on the Bivalve Anadara subcrenata.

Single and joint oxidative stress of cadmium (Cd) and phenanthrene (Phe) on Anadara subcrenata were investigated under laboratory conditions with biomarkers such as reactive oxygen species (ROS), malondialdehyde (MDA), superoxide dismutase (SOD) and total antioxidant capacity (TAOC). The results indicated that the ROS level in Anadara subcrenata exposed to Cd and Phe significantly (P < 0.05) increased during the early exposure stage, and the TAOC level and SOD activity were induced as the response of the antioxidant defense system, and this followed a damage, recovery or acclimation event. The MDA content was negatively correlated with SOD activity. As the time went on, the ROS level decreased gradually and was close to that in the control after 9 days; the TAOC level decreased accordingly, but the recovery rate of the SOD activity was slower than that of the TAOC level. High concentrations of Cd or Phe had a stronger oxidative stress effect on Anadara subcrenata. Phe had a stronger effect on the SOD activity of Anadara subcrenata. The joint effects of Cd and Phe on the levels of ROS and TAOC, SOD activity and MDA content in Anadara subcrenata are dependent on their concentration combination, which were called the double-dose dependent effects and time-dependent effects, respectively. The binary mixture treatments of 477.33 µg/L Cd and 48.08 µg/L Phe had the highest oxidative stress on Anadara subcrenata.

The effect of bioturbation by polychaete Perinereis aibuhitensis on release and distribution of buried hydrocarbon pollutants in coastal muddy sediment.

As a headdown deposit feeder, polychaete Perinereis aibuhitensis may transport particles from the deep sediment layers to the surface enhancing sediment resuspension, which influences the fate of sediment-associated pollutants. The impact of P. aibuhitensis on the remobilization of buried hydrocarbons was investigated through a 30 day laboratory microcosm experiment with hydrocarbon spiked sediment buried in different layers. The bioturbation of P. aibuhitensis enhanced sediment resuspension by approximately fourfold suspended particulate matters (SPM) and twofold dissolved organic carbon (DOC) in bioturbation (BI) microcosms (added P. aibuhitensis) than control (CL) microcosms (without P. aibuhitensis). The release of buried hydrocarbons were also enhanced with significantly higher hydrocarbon concentrations in BI microcosms than CL and blank (BK) microcosms (without spiked hydrocarbons). The presence of P. aibuhitensis led to the transport of buried spiked hydrocarbons in sediment and enhanced the loss of buried hydrocarbons.

Distribution, sources and ecological risk assessment of PAHs in surface seawater from coastal Bohai Bay, China.

The distribution, composition, potential sources and ecological risk of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) were investigated in surface water from coastal Bohai Bay. The PAH concentrations ranged from 48.0 to 607 ng L-1 with the mean value of 267 ng L-1 in dissolved phase and 198 to 935 ng L-1 with the mean value of 424 ng L-1 in particle-associated phase, and decreased following the order: Qinhuangdao (QHD) > Caofeidian (CFD) > Huanghuagang (HHG). The 2-3 ring PAHs accounted for 79.9% to 86.2% in particle-associated phase and 65.6% to 73.2% in dissolved phase of total 16 PAHs, in which naphthalene (Nap) was the most dominant compound. The PAHs in surface seawater mainly originated from petrogenic sources according to the molecular ratios of benzo[a]anthracene/228 and fluoranthene/202. Risk quotients indicated that there was potential ecological risk for PAHs in surface seawater, especially for pyrene and fluorene.

Enhanced removal of sediment-associated total petroleum hydrocarbons under bioturbation by polychaete perinereis aibuhitensis.

Bioturbation processes could influence the physical, chemical and biological properties of aquatic sediments and improve the mineralization of organic matter in sediment. The influence of bioturbation by polychaete Perinereis aibuhitensis on the removal of sediment-associated total petroleum hydrocarbon (TPH) was evaluated through laboratory experiment with P. aibuhitensis cultured in crude oil contaminated coastal sediment. After 60 days, the TPH concentrations in the sediments were significantly decreased compared to the initial concentrations, in which the TPH concentrations in bioturbation experiments (with worms) were significantly lower than those in control experiments (without worms) for both low (1.48 ± 0.19g/kg dry wt) and high (2.67 ± 0.33 g/kg dry wt) TPH-contaminated groups, indicating bioturbation enhanced the removal of TPH in sediment. The TPH removal rates in high TPH group were significantly lower than those in low TPH group, suggested that petroleum pollution inhibited the degradation of petroleum hydrocarbons in sediment. However, the stimulation efficiency was higher in high TPH group than that in low TPH group, which may be the result of enhanced hydrocarbon's bioavailability by digestive fluid during gut transit.

Graphene oxide in the marine environment: Toxicity to Artemia salina with and without the presence of Phe and Cd2.

Given the increasing potential of graphene oxide entering marine environments, it is imperative to assess the risks of GO on marine ecosystem, including its direct toxicity to marine organisms and indirect toxicity brought by co-existing aquatic pollutants, as a result of the remarkable adsorption capacity of GO. In the present study, the acute toxicity of GO, Phe, Cd2+, GO-Phe, and GO-Cd2+ to Artemia salina were systemically assessed and compared for the first time. Although the lethal effects of GO alone to A. salina only appeared at high GO dose (500 mg/L), its sublethal toxicity (growth inhibition) at concentrations as low as 1 mg/L was observed by microscopy, which was likely closely related to the GO-induced oxidative stress in A. salina. Compared with the toxicity of Phe alone, GO-Phe exhibited a synergistic effect to A. salina at a high GO concentration. For GO-Cd2+, the toxicity was positively correlated with both GO dose and Cd2+ dose. The increased toxicity of GO-Phe or GO-Cd2+ at high doses might be attributed to the promoted bioaccumulation of toxicants by GO, as the adhesion of GO complexes to intestinal tract of A. salina was observed during the toxicity tests, which probably resulted in further toxicological effects.

TiO2 nanoparticles in the marine environment: Impact on the toxicity of phenanthrene and Cd2+ to marine zooplankton Artemia salina.

The impact of manufactured nanoparticles on the toxicity of co-existing pollutants in aquatic environments has raised increasing concerns. However, the toxicity of polycyclic aromatic hydrocarbons or metal ions in the presence of titanium dioxide nanoparticles (nTiO2) to marine zooplankton has been rarely reported. In the present study, the impacts of nTiO2 on the toxicity of phenanthrene (Phe) and cadium (Cd2+) to Artemia salina, a model marine zooplankton, were investigated. Although nTiO2 alone exerted a limited toxicity to A. salina within 48h of exposure, nTiO2 strongly altered the toxicity of Phe and Cd2+ to A. salina. Compared with the individual toxicities of pollutants to A. salina, the toxicities of Phe and Cd2+ increased by 2.0% and 12.2%, respectively, in the presence of 5mg/L nTiO2, but decreased by 24.5% and 57.1%, respectively, in the presence of 400mg/L nTiO2. These concentration-dependent impacts of nTiO2 on the toxicity of Phe or Cd2+ might be attributed to the concurrent functions of several interrelated factors including the adsorption of pollutants on nTiO2, the nTiO2-faciliated bioaccumulation of pollutants, the limited gut volume in organisms, and the aggregation and sedimentation behaviors of nTiO2. These results presented in the study could help understand the effects of manufactured nanomaterials in marine environments.

Pollution characteristics and ecological risk assessment of HCHs and DDTs in estuary wetland sediments from the Bohai Bay, North China.

Hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) tend to persist in the environment for long periods of time. The concentration and distribution of HCHs and DDTs were investigated in surface sediments of Yongdingxinhe wetland and Binhai wetland by gas chromatography-mass spectrometer (GC-MS). All isomers of HCHs and DDTs were detected in all of the samples. The concentrations of total HCHs (ΣHCHs) in two wetland sediments ranged from 69.81 to 379.28 ng · g -1, with a mean value of 224.55 ng · g -1. The concentrations of total DDTs (ΣDDTs) ranged from 98.32 to 129.10 ng · g -1, with a mean value of 113.71 ng · g -1. The results of an ecological risk assessment demonstrated that there was high-risk ecological effect of organochlorine pesticides (OCPs) on the estuary wetlands. Lindane and technical DDTs were found to be the main sources of OCPs.

Effects of nano-TiO2 on perfluorooctanesulfonate bioaccumulation in fishes living in different water layers: Implications for enhanced risk of perfluorooctanesulfonate.

Nano-titanium dioxide (nano-TiO2) is one of the most universal engineered nano-materials while perfluorooctanesulfonate (PFOS) is a typical new persistent organic pollutant. They are widely used and present in aquatic environment. In this study, a novel semi-static multilayer microcosm was setup to investigate the impacts of nano-TiO2 on PFOS bioaccumulation in fish species [Danio rerio (D. rerio), Ctenopharyngodon idella (C. idella), Hypostomus plecostomus (H. plecostomus)] living in different vertical layers. As a result of aggregation and deposition, the concentration of TiO2 increased from upper to bottom layers in the water column. Concomitantly, due to adsorption of PFOS on the nano-TiO2 particles, PFOS also displayed an increasing trend from upper to bottom layer. Owing to ingestion of the TiO2-PFOS complexes, more PFOS was taken-up by fish. With the aid of intestinal fluid, PFOS was readily released from TiO2 particles and absorbed by fish. As a result, accumulation of PFOS in whole fish was facilitated and the bioaccumulation factors of PFOS in D. rerio, C. idella and H. plecostomus were 3.01, 2.42 and 1.11 times of that in the groups without TiO2. However, TiO2 aggregates were too large to penetrate biological membranes to participate body circulation, and no significant accumulation of TiO2 was observed in fish muscle. The results suggested that the ecological risk of PFOS could be enhanced due to the presence of nano-TiO2 in water.

Bioaccumulation and biotransformation of polybrominated diphenyl ethers in the marine bivalve (Scapharca subcrenata): influence of titanium dioxide nanoparticles.

Titanium dioxide nanoparticles (nTiO2) have the potential to adsorb co-existing contaminants in aqueous environment to form nanoparticle-contaminant complexes. Adsorption by nTiO2 might impact the fate of contaminants in water. Bioaccumulation experiments were conducted to compare the accumulation of polybrominated diphenyl ethers (PBDEs) in marine bivalve (Scapharca subcrenata) exposed to PBDEs in the presence and absence of nTiO2. PBDEs can be taken up by S. subcrenata through aqueous exposure. nTiO2 acts as a carrier and can enhance the ingestion of PBDEs, but the bioaccumulation of PBDEs was not facilitated significantly in the presence of nTiO2. Similar accumulation kinetics pattern was found after exposing to PBDEs in the presence and absence of nTiO2. Further analysis showed that no significant difference between the congener profiles of PBDEs in the presence and absence of nTiO2, suggesting that nTiO2 would not influence the biotransformation of PBDEs in clams.

Titanium dioxide nanoparticles as carrier facilitate bioaccumulation of phenanthrene in marine bivalve, ark shell (Scapharca subcrenata).

To evaluate the impact of titanium dioxide nanoparticles (nTiO2) on the uptake of hydrophobic organic chemicals by marine bivalves, we conducted a comparative bioaccumulation study by exposing clam, Scapharca subcrenata, to phenanthrene (Phe) in the presence and absence of nTiO2. The large surface area of nTiO2 resulted in adsorption of co-existing Phe in aqueous solution to form nTiO2-Phe complexes. Accumulation of nTiO2 was not observed in clams at exposed concentration (500 µg/L) in this study. However, enhanced uptake of Phe by clams was observed in the presence of nTiO2, with ku and BAFs values being 2 and 1.7 times higher than that of Phe alone, respectively. The enhanced uptake can be explained by ingestion of nTiO2-Phe complexes into the gut and subsequent desorption of Phe there. Therefore, nTiO2 as a carrier facilitated the uptake of Phe by marine bivalves.

Toxicity assessment of iron oxide nanoparticles in zebrafish (Danio rerio) early life stages.

Iron oxide nanoparticles have been explored recently for their beneficial applications in many biomedical areas, in environmental remediation, and in various industrial applications. However, potential risks have also been identified with the release of nanoparticles into the environment. To study the ecological effects of iron oxide nanoparticles on aquatic organisms, we used early life stages of the zebrafish (Danio rerio) to examine such effects on embryonic development in this species. The results showed that ≥10 mg/L of iron oxide nanoparticles instigated developmental toxicity in these embryos, causing mortality, hatching delay, and malformation. Moreover, an early life stage test using zebrafish embryos/larvae is also discussed and recommended in this study as an effective protocol for assessing the potential toxicity of nanoparticles. This study is one of the first on developmental toxicity in fish caused by iron oxide nanoparticles in aquatic environments. The results will contribute to the current understanding of the potential ecotoxicological effects of nanoparticles and support the sustainable development of nanotechnology.

Bioaccumulation and distribution of perfloroalkyl acids in seafood products from Bohai Bay, China.

Ten perfluoroalkyl acids (PFAAs) were measured in seafood collected from Bohai Bay, China in 2010. The summed concentrations of the PFAAs were in the ranges of not detected to 194 ng/g dry weight and 4.0 to 304 ng/g dry weight for invertebrates and fish, respectively. The levels of perflurooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the seafood were lower than those from North America, the Mediterranean Sea, and South Korea. Living habitat, trophic level, and feeding habits had important impacts on the bioaccumulation and distribution of PFAAs in the seafood. The species at higher trophic levels had the potential to accumulate more PFAAs than benthic invertebrates. Tidal-flat organisms tended to accumulate more PFOA than PFOS, whereas the opposite was seen for shallow-water species. For all the species, PFOS and PFOA were partitioned preferentially in the liver or viscera. Risk assessment indicated that the current level of PFAAs in the seafood of Bohai Bay does not represent an immediate source of harm to public health.

Bioaccumulation and metabolism of polybrominated diphenyl ethers in carp (Cyprinus carpio) in a water/sediment microcosm: important role of particulate matter exposure.

Microcosms were built up to simulate a pond system with polybrominated diphenyl ether (PBDE) contaminated sediment and bioorganisms. The microcosms were divided into groups A and B. In group A, both benthic invertebrates (tubificid worms) and carp (Cyprinu carpio) were added, while in group B, only fish were added. After exposure for 20 d, the fish were sampled (exposure I). A net was fixed in the microcosms, and new fish were added (exposure II). These fish were prohibited from contacting the sediment by the net, and the accumulation and depuration of PBDEs in the fish were investigated. Among 11 monitored PBDE congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, BDE-206, BDE-207, BDE-208, and BDE-209), only 5 congeners (BDE-28, BDE-47, BDE-100, BDE-153, and BDE-154) were detected in the carp fillets and liver. BDE-99 and BDE-183 were not detected in the fish because of the efficient metabolic debromination in carp tissues. The uptake of PBDEs in exposure I was significantly higher/faster than that in exposure II, since the fish in exposure I had an opportunity to take in more of the highly contaminated particles. The uptake kinetics (k(s)) and elimination (k(e)) rate coefficients showed a general trend of decreasing with increasing log K(ow). No significant difference was observed in uptake/depuration kinetics between groups A and B, indicating that the tubificids' reworking does not affect the bioaccumulation of sediment-associated PBDEs in fish significantly. All the PBDE congeners, including nona- and deca-BDEs, were bioaccumulated in the tubificid worms. The PBDE concentrations in the worms were significantly higher than those in the fish, and the congener profile of the sevem major congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) was distinctly different from that of fish tissues. The biota-sediment accumulation factors in the worms ranged from 0.01 to 5.89 and declined with increasing bromination and log K(ow.).

Predicting the bioavailability of sediment-associated polybrominated diphenyl ethers using a 45-d sequential Tenax extraction.

A 45-d Tenax extraction was used to evaluate the bioavailability of polybrominated diphenyl ethers (PBDEs) in three spiked sediments. The effect of aging on desorption kinetics of PBDEs was investigated by incubating one of the sediments for 7, 14, 30 and 60 d at room temperature. Desorption kinetics were well described by a three-compartment model. The fraction of very slow desorption (Fvs) contributed the most of the desorbed PBDEs from sediments. The total desorption amount of PBDEs decreased with the increase of total organic carbon in the sediments, suggesting that organic matter is an important factor controlling the partition of PBDEs in sediments. The total desorption amount of PBDEs decreased while log [(Fslow+Fvs)/Frap] increased with logKow of PBDE congeners, indicating that the bioavailability of PBDEs in sediment decreases with logKow of the congeners. As the residential time of PBDEs in the sediment increased from 7 to 60 d, Frap of individual PBDE congeners decreased gradually with simultaneous increase of Fvs. There was a good positive correlation between Frap and F6/F24, indicating that either 6 h or 24 h Tenax extraction could be a proxy for Frap and bioavailability. In general, the results in present study suggest that the bioavailability of nona- and deca-BDEs in sediment is very low due to their strong hydrophobicity and large molecular size.

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete).

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K(s)) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d(-1)), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.

Bioaccumulation and distribution of polybrominated diphenyl ethers in marine species from Bohai Bay, China.

Polybrominated diphenyl ethers (PBDEs) were analyzed in invertebrate and fish species collected from Bohai Bay, China in 2007 to 2008. The concentrations of the 16 detected PBDE congeners were in the range of 1.4 to 425 and 2.9 to 767 ng/g lipid for invertebrates and fish, respectively. The summed concentrations of the six major PBDE congeners (BDE-28, 47, 99, 100, 153, 154) (Σ(6)PBDEs) in fish were significantly higher than in invertebrates, while demersal fish concentrations were higher than pelagic fish. The congeners BDE-47, 99, and 100 contributed more in viscera or liver than in muscle, indicating that the metabolic capability of the viscera or liver is greater than that of muscle. The ratio of BDE-47/99 was relatively higher in fish than in invertebrate samples, suggesting a more developed metabolism capacity in fish. Polybrominated diphenyl ether congeners tend to accumulate in viscera or liver rather than in muscle. The fully brominated congener BDE-209 was detected in some species, suggesting that it can be accumulated by organisms. Uptake from sediment may be the major uptake pathway for most brominated PBDEs in benthic species.