Concentration distribution and potential health risk of heavy metals in Mactra veneriformis from Bohai Bay, China.

To investigate the pollution level and evaluate the potential health risks of heavy metals, the concentrations of chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), antimony (Sb), and lead (Pb) were determined by inductively coupled plasma-mass spectrometry (ICP-MS) in 198 clams (Mactra veneriformis) collected from 11 sites of the Bohai Bay. The results showed that heavy metal concentrations in the clams were different at different sites (p<0.05). Mn was dominant with a percentage of 22.08-77.03% in heavy metals, followed by Zn with 12.66-57.11%, and the concentration of Pb was the lowest with 0.45-1.04%. The potential health risk to consumers was evaluated by the target hazard quotient (THQ) and the maximum daily consumption rate (CRmax). The results indicated that the THQs of Co were the highest with the values of 1.125, 1.665, and 1.144 at three sections; the values of other individual metals were <1, which indicated that consumption of clams from the study areas caused health risks due to Co. Moreover, the CRmax values also indicated the potential health risk caused by Co in clams consumed in this area. Pearson correlation analysis and principal component analysis (PCA) indicated that there were significantly positive or negative correlations between the heavy metals (p<0.05), and the studied metals were divided into four groups. The results indicated that the concentrations of heavy metals in clams were affected not only by pollution sources but also by the characteristics of clams that could absorb selectively and accumulate special metals. This study offers important information on the pollution levels of heavy metals in clams and warns consumers of the health risks associated with the consumption of clams in the area.

Polycyclic aromatic hydrocarbons and organochlorine pesticides in rice hull from a typical e-waste recycling area in southeast China: temporal trend, source, and exposure assessment.

The residue levels of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) and 16 selected organochlorine pesticides (OCPs) in rice and rice hull collected from a typical e-waste recycling area in southeast China were investigated from 2005 to 2007. PAHs and OCPs also were measured in ten mollusk species (soft tissues) collected in an adjacent bay in 2007. Individual PAHs were frequently found in the entire sample set (including the rice, hull, and mollusk samples) with a detection rate of 73 %. The total concentrations of 16 PAHs (ΣPAHs) and 16 OCPs (ΣOCPs) were in the range of 40.8-432 ng/g dry weight (mean: 171 ng/g) and 2.35-925 ng/g (122 ng/g), respectively, which were comparable or higher than those reported in some polluted areas. Statistical comparisons suggested that the concentrations of contaminants in hull gradually decreased from 2005 to 2007 and the residue levels were generally in the order of mollusk, hull, and rice, on a dry weight basis. Principal component analysis in combination with diagnostic ratios implied that combustion of coal, wood, and plastic wastes that are closely associated with crude e-waste recycling activities is the main source of PAHs. The finding of decreasing trend of concentrations of PAHs in this area is consistent with the efforts of local authorities to strengthen regulations on illegal e-waste recycling activities. Composition analysis suggested that there is a recent usage or discharge of hexachlorocyclohexane and dichlorodiphenyltrichloroethane into the tested area. The estimated daily intake (EDI) of ΣPAHs and ΣOCPs (calculated from mean concentrations) through rice and mollusk consumption was 0.411 and 0.921 µg/kg body weight (bw)/day, respectively.

Occurrence and profiles of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in soils from a typical e-waste recycling area in Southeast China.

Surface soils collected from Taizhou, a typical e-waste recycling area in Southeast China, were analyzed for the residues of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) by using microwave-assisted extraction and gas chromatography -mass spectrometry (GC-MS). The total concentrations of 16 PAHs in US EPA's priority list (ΣPAHs), six indicator PCBs (ΣPCBs), 15 OCPs widely used in China (ΣOCPs) in soils ranged from 125 to 4737 ng/g (average: 854 ng/g), from not detected to 55.4 ng/g (3.16 ng/g), and from 47.9 to 820 ng/g (276 ng/g), respectively. Individual PAHs were ubiquitously found in soil samples with detected ratio of 96% and their residual levels were comparable with those of serious polluted sites. Principal component analysis in combination with diagnostic ratios suggested that the combustion of coal, wood, and plastic wastes that are closely associated with illegal and unsafe recycling operations of e-wastes was the main source of PAHs in this area. Compared with other polluted sites, the PCBs residues in soils were generally low except for those in the major recycling site. The residual levels of OCPs in this region were also relatively higher and hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its metabolite forms including dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE), hexachlorobenzene (HCB), and dicofol were dominant species. The composition analysis indicated that the HCHs residues in soils might originate from the application of lindane (pure Î³-HCH) and parts of DDTs possibly from the wide use of dicofol with high impurity of DDT compounds in this region.

Bamboo charcoal as adsorbent for SPE coupled with monolithic column-HPLC for rapid determination of 16 polycyclic aromatic hydrocarbons in water samples.

The coupling of solid-phase extraction (SPE) using bamboo charcoal (BC) as an adsorbent with a monolithic column-high performance liquid chromatography (MC-HPLC) method was developed for the high-efficiency enrichment and rapid determination of 16 polycyclic aromatic hydrocarbons (PAHs) in water. Key influence factors, such as the type and the volume of the elution solvent, and the flow rate and the volume of the sample loading, were optimized to obtain a high SPE recovery and extraction efficiency. BC as an SPE adsorbent presented a high extraction efficiency due to its large specific surface area and high adsorption capacity; MC as an HPLC column accelerated the separation within 8 min because of its high porosity, fast mass transfer, and low-pressure resistance. The calibration curves for the PAHs extracted were linear in the range of 0.2-15 µg/L, with the correlation coefficients (r(2)) between 0.9970-0.9999. This method attained good precisions (relative standard deviation, RSD) from 3.5 to 10.9% for the standard PAHs I aqueous solutions at 5 µg/L; the method recoveries ranged in 52.6-121.6% for real spiked river water samples with 0.4 and 4 µg/L. The limits of detection (LODs, S/N = 3) of the method were determined from 11 and 87 ng/L. The developed method was demonstrated to be applicable for the rapid and sensitive determination of 16 PAHs in real environmental water samples.

Asporyergosterol, a new steroid from an algicolous isolate of Aspergillus oryzae.

Asporyergosterol (1), a new steroid with an E double bond between C-17 and C-20, was identified from the culture extracts of Aspergillus oryzae, an endophytic fungus isolated from the marine red alga Heterosiphonia japonica. Moreover, four known steroids including (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (2), (22E,24R)-3beta-hydroxyergosta-5,8,22-trien-7-one (3), (22E,24R)-ergosta-7,22-dien-3beta,5alpha,6beta-triol (4), and (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (5) were isolated. Structures of these compounds were unambiguously established by spectroscopic techniques and by comparison with literature values. All the isolates exhibited low activity to modulate acetylcholinesterase (AChE).

Indoloditerpenes from an algicolous isolate of Aspergillus oryzae.

Two new indoloditerpene derivatives asporyzin A (1) and asporyzin B (2), one new indoloditerpene asporyzin C (3), and three known related indoloditerpenes JBIR-03 (4), emindole SB (5), and emeniveol (6) were isolated from an endophytic fungus Aspergillus oryzae, isolated from the marine red alga Heterosiphonia japonica. Their structures were unambiguously established by spectroscopic techniques. In addition, all the isolates were evaluated preliminarily for insecticidal and antimicrobial activities in order to probe into their chemical defensive function. Compound 4 was more active against brine shrimp than the others, and 3 possessed potent activity against Escherichia coli.

Toxicology mechanism of the persistent organic pollutants (POPs) in fish through AhR pathway.

With the development of industry and agriculture, the cases of cancer and tumor have been increasing gradually in the last 30 years, and quite a few cases are caused by persistent organic pollutants (POPs), some of them belonging to environmental endocrine disruptors, and they have become ubiquitous in the environment, especially in the aquatic ecosystem; so this issue has aroused the extensive attention of the world. The mechanism of POPs toxicology is very complicated, but it is mainly mediated by the aryl hydrocarbon receptor (AhR) pathway in fish. In order to gain a comprehensive understanding of the AhR pathway, the present paper focuses on reviewing it from four major steps, including formation of cytosolic complex, translocation of AhR, heterodimerization of AhR, and induction of CYP1A. This study summarized the isoform numbers of AhR pathway genes and the expression patterns in the regulation process of POPs toxicology in zebrafish.

Identification and characterization of an intracellular Cu, Zn-superoxide dismutase (icCu/Zn-SOD) gene from clam Venerupis philippinarum.

Superoxide dismutase (SOD, EC 1.15.1.1) represents one kind of enzyme involved in scavenging the high level of reactive oxygen species (ROS) into molecular oxygen and hydrogen peroxide. In the present study, the intracellular Cu/Zn-SOD gene (icCu/Zn-SOD) of Venerupis philippinarum (denoted as VpSOD) was identified from haemocytes by homology cloning and RACR approaches. The full-length cDNA of VpSOD consisted of 910 nucleotides with a canonical polyadenylation signal sequence AATAAA, a polyA tail, and an open-reading frame of 465 bp encoding 154 amino acids. The deduced amino acid of VpSOD shared high similarity with the icCu/Zn-SODs from other species, indicating that VpSOD should be a new member of icCu/Zn-SOD family. Several highly conserved motifs including Cu, Zn binding sites (H(46), H(48), H(63), H(120) for Cu binding, and H(63), H(71), H(80), D(83) for Zn binding), intracellular disulfide bond and two Cu, Zn SOD signatures were also identified in VpSOD. The temporal expression of VpSOD in haemocytes after Vibrio anguillarum challenge was recorded by quantitative real-time RT-PCR. The relative expression level of VpSOD mRNA was up-regulated rapidly at 6 h post-infection and reached 18-fold of the control group. After a drastic decrease at 12 h, the expression level increased again and reached 22-fold to that in the control group at 96 h post-infection. All these results indicated that VpSOD was an acute-phase protein involved in the immune responses of V. philippinarum.

Synthesis and moisture absorption and retention activities of a carboxymethyl and a quaternary ammonium derivative of alpha,alpha-trehalose.

Carboxymethyl alpha,alpha-trehalose (CMT) and a quaternary ammonium derivative of alpha,alpha-trehalose (QT) were successfully prepared, and their moisture absorption and retention activities were assessed. Results showed that both CMT and QT had better moisture absorption abilities at 43% and 81% relative humidity (RH) than alpha,alpha-trehalose. In addition, the two alpha,alpha-trehalose derivatives had better moisture retention abilities than alpha,alpha-trehalose under three humidity conditions: 81% RH, 43% RH, and under dry conditions. Therefore, carboxymethylation and quaternarization could improve the moisture absorption and retention abilities of alpha,alpha-trehalose. CMT and QT showed better moisture absorption ability and moisture retention ability than that of hyaluronan (HA), and could potentially find a use as moisture retention ingredient, for example, in cosmetics.

Molecular phylogenies and evolutionary behavior of AhR (aryl hydrocarbon receptor) pathway genes in aquatic animals: implications for the toxicology mechanism of some persistent organic pollutants (POPs).

Phylogenetic analysis of AhR pathway genes and their evolutionary rate variations were studied on aquatic animals. The gene sequences for the proteins involved in this pathway were obtained from four major phylogenetic groups, including bivalvia, amphibian, teleostei and mammalia. These genes were distributed under four major steps of toxicology regulation: formation of cytosolic complex, translocation of AhR, heterodimerization of AhR and induction of CYP1A. The NJ, MP, and ML algorithm were used on protein coding DNA sequences to deduce the evolutionary relationship for the respective AhR pathway gene among different aquatic animals. The rate of non-synonymous nucleotide substitutions per non-synonymous site (d(N)) and synonymous nucleotide substitutions per synonymous site (d(S)) were calculated for different clade of the respective phylogenetic tree for each AhR pathway gene. The phylogenetic analysis suggests that evolutionary pattern of AhR pathway genes in aquatic animals is characterized mainly through gene duplication events or alterative splicing. The d(N) values indicate that all AhR pathway genes are well conserved in aquatic animals, except for CYP1A gene. Furthermore, compare with other aquatic animals, the d(N) value indicates that AhR pathway genes of fish are less conserved, and these genes likely go through an adaptive evolution within aquatic animals.

Brominated selinane sesquiterpenes from the marine brown alga Dictyopteris divaricata.

Two new brominated selinane sesquiterpenes, 1-bromoselin-4(14),11-diene (1) and 9-bromoselin-4(14),11-diene (2), one known cadinane sesquiterpene, cadalene (3), and four known selinane sesquiterpenes, alpha-selinene (4), beta-selinene (5), beta-dictyopterol (6), and cyperusol C (7), were isolated from a sample of marine brown alga Dictyopteris divaricata collected off the coast of Yantai (China). Their structures were established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.

A new cadinane sesquiterpene from the marine brown alga Dictyopteris divaricata.

A sample of the marine brown alga D. divaricata collected off the coast of Yantai (P.R. China) was dried, powdered, and extracted with the mixture of CHCl(3) and MeOH (1:1, v/v). By a combination of silica gel and Sephadex LH-20 column chromatography and preparative TLC, a new cadinane sesquiterpene 1,4-epoxymuurolan-5beta-ol (1) was isolated from this species. Its structure was established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.

A new epoxy-cadinane sesquiterpene from the marine brown alga Dictyopteris divaricata.

A new epoxy-cadinane sesquiterpene, 4beta,5beta-epoxycadinan-1beta-ol (1), and six known cadinane sesquiterpenes: cadinan-1,4,5-triol (2), 4alpha,5beta-dihydroxycubenol (3), cubenol (4), cadinan-3-ene-1,5-diol (5), cubenol-3-one (6), and torreyol (7), were isolated from a sample of marine brown alga Dictyopteris divaricata collected off the coast of Yantai (China). Their structures were established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.