Interactive effects of hypoxia and polybrominated diphenyl ethers (PBDEs) on microbial community assembly in surface marine sediments

Hypoxia alters the oxidation–reduction balance and the biogeochemical processes in sediments, but little is known about its impacts on the microbial community that is responsible for such processes. In this study, we investigated the effects of hypoxia and the ubiquitously dispersed flame-retardant BDE47 on the bacterial communities in marine surface sediments during a 28-days microcosm experiment. Both hypoxia and BDE47 alone significantly altered the bacterial community and reduced the species and genetic diversity. UniFrac analysis revealed that BDE47 selected certain bacterial species and resulted in major community shifts, whereas hypoxia changed the relative abundances of taxa, suggesting slower but nonetheless significant community shifts. These two stressors targeted mostly different taxa, but they both favored Bacteroidetes and suppressed Gammaproteobacteria. Importantly, the impacts of BDE47 on bacterial communities were different under hypoxic and normoxic conditions, highlighting the need to consider risk assessments for BDE47 in a broader context of interaction with hypoxia.     

Endocrine effects of methoxylated brominated diphenyl ethers in three in vitro models

Methoxylated brominated diphenyl ethers (MeO-BDEs) in aquatic environments have been found to be primarily of natural origin in the marine environment and not from biotransformation of synthetic PBDEs. Two of the eight MeO-PBDEs (2′-MeO-BDE-68 and 6-MeO-BDE-47) that were detected in anchovy from the Yangtze River Delta, were natural products from marine organisms. So 2′-MeO-BDE-68 and 6-MeO-BDE-47 were chosen to study the potential to modulate androgen, estrogen, or thyroid hormone receptor- (AR, ER, ThR) mediated responses by use of reporter gene assays. 2′-MeO-BDE-68 was antiandrogenic at 50 μM, estrogenic at 10 μM and antiestrogenic at 10 and 50 μM (IC₅₀ = 4.88 μM). 2′-MeO-BDE-68 enhanced luciferase expression by 5 nM T3 at 50 μM. 6-MeO-BDE-47 exhibited potent antiandrogenicity at 1 μM and greater (IC₅₀ = 41.8 μM) and possessed estrogenic activity at 10 μM and antiestrogenic activity at 10 and 50 μM (IC₅₀ = 6.02 μM).     

Concentration of polybrominated diphenyl ethers (PBDEs) in sediment cores of Sundarban mangrove wetland, northeastern part of Bay of Bengal (India)

The paper presents the first comprehensive survey of congener profiles (12 congeners) of polybrominated diphenyl ethers (PBDEs) in core sediment samples (<63 microm) covering seven sites in Sundarban mangrove wetland (India). Gas-chromatographic analyses were carried out in GC-Ms/Ms for tri- to hepta- brominated congeners. Results pointed out a non-homogenous contamination of the wetland with summation operator(12) PBDE values ranging from 0.08 to 29.03 ngg(-1), reflecting moderate to low contamination closely in conformity to other Asian aquatic environments. The general order of decreasing congener contribution to the total load was: BDE 47>99>100>154, similar to the distribution pattern worldwide. Although tetrabromodiphenyl ether BDE 47 was found in all samples followed by hexabromodiphenyl ether BDE-154, they were not necessarily the dominant congeners. No uniform temporal trend on PBDE levels was recorded probably due to particular hydrological characteristics of the wetland and/on non-homologous inputs from point sources (untreated municipal wastewater and local industries, electronic wastes from the dump sites, etc.) of these compounds. Because of the propensity of PBDEs to accumulate in various compartments of wildlife and human food webs, evaluation of biological tissues should be undertaken as a high priority.     

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.     

PCB, PCDD/F and PBDE levels and profiles in crustaceans from the coastal waters of Brittany and Normandy (France)

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analysed in the muscle of various edible marine crustaceans (spider crab, edible crab, velvet swimming crab and Norway lobster) from the Brittany and Normandy coasts (France). The highest concentrations were measured in species collected from Antifer (Seine Bay). PCB and PBDE patterns in crustacean muscles were similar and independent of the geographical area with the predominance of the high chlorinated PCBs (CB153, 138, 118 and 180), and of a few PBDE congeners (BDE47, BDE99, BDE100 and BDE28). Oppositely, dioxin contamination differed with site. The major component in crustaceans from the Seine Bay was 2378-TCDF, whereas specimens from cleaner areas had higher relative concentrations of OCDD. Finally, the comparison of the spider crab contaminant profiles to those measured in mussel and sea bass highlighted two different trends: decapod crustaceans possess relatively strong capacity to metabolise PCBs and PBDEs; however these species might be used as bioindicators for dioxin pollution monitoring in the marine coastal environment.     

Geological controls on groundwater chemistry and arsenic mobilization: Hydrogeochemical study along an E–W transect in the Meghna basin, Bangladesh

Hydrogeochemical investigations along an E–W transect in the middle Meghna basin show groundwater chemistry and redox condition vary considerably with the change in geology. Groundwater in the Holocene shallow (<150 m bgl) alluvial aquifer in western part of the transect is affected by high arsenic concentration (As > 10 μg/l) and salinity. On the other hand, groundwater from the Pliocene Dupi Tila sandy aquifer in the eastern part is fresh and low in As (<10 μg/l). The Holocene shallow aquifers are high in dissolved As, , Fe and dissolved organic carbon (DOC), but generally low in and . High concentrations (250–716 mg/l) together with high DOC concentrations (1.4–21.7 mg/l) in these aquifers reflect active sources of degradable natural organic matter that drives the biogeochemical process. There is generally de-coupling of As from other redox-sensitive elements. In contrast, the Pliocene aquifers are low in As, and DOC. Molar ratio of /H₄SiO₄ suggests that silicate weathering is dominant in the deeper Holocene aquifers and in the Pliocene aquifers. Molar ratios of Cl⁻/ and Na⁺/Cl⁻ suggest mixing of relict seawater with the fresh water as the origin of groundwater salinity. Speciation calculations show that saturation indices for siderite and rhodochrosite vary significantly between the Holocene and Pliocene aquifers. Stable isotopes (δ²H and δ¹⁸O) in groundwater indicate rapid infiltration without significant effects of evaporation. The isotopic data also indicates groundwater recharge from monsoonal precipitation with some impact of altitude effect at the base of the Tripura Hills in the east. The results of the study clearly indicate geological control (i.e. change in lithofacies) on groundwater chemistry and distribution of redox-sensitive elements such as As along the transect.     

地脉动在系舟山北麓断裂次级断裂探测中的应用

系舟山北麓断裂为1038年定襄■级地震的发震构造，在盆地内部可能存在一条或多条次级断裂，并有可能非常邻近忻州城区，使用地脉动方法对系舟山北麓断裂是否存在次级隐伏断裂进行探测。通过共振频率的横向变化以及基岩深度和频率的关系获得了约17个比较显著的断点位置，指示出系舟山山前存在三条比较显著的次级断裂，以及它们的断点位置、相对错距和相应的走向分布，为忻州市区防震减灾提供基础资料。     

PBDEs, methoxylated PBDEs and HBCDs in Japanese common squid (Todarodes pacificus) from Korean offshore waters

Little information is available on the levels of brominated compounds found in biota from the Korean Peninsula. In this study, Japanese common squids (Todarodes pacificus) were analyzed for 38 polybrominated diphenyl ethers, two methoxylated polybrominated diphenyl ethers and three stereoisomers of hexabromocyclododecane (α, β, and γ-HBCD) from the east and western coasts of the Korean Peninsula. Among 38 PBDEs, 10 PBDEs were detected and their total concentrations ranged from 21 to 292 ng/g lipid wt with a mean concentration of 108 ng/g lipid wt, while two MeO-BDEs and three isomers of HBCDs were detected in all samples. BDE47 showed the highest residual level, followed by BDE99, 154, 153, 28/33. Concentrations of PBDEs and MeO-BDEs were not significantly different between the both sides of the Korean Peninsula; however, HBCD concentrations were higher levels in the East/Japan Sea than the Yellow Sea, indicating that HBCD sources possibly exist in Japan.     

Comparing grain size distribution of sediment and original soil under raindrop detachment and raindrop-induced and flow transport mechanism

The grain size distribution (GSD) of sediment in comparison with the original soil GSD is discussed under different slopes (5, 15 and 25%) and rainfall intensities (30, 60 and 90 mm h^–1 with respective duration of 30, 15 and 10 min) but identical runoff (15 mm). The sediment quantification was carried out by raindrop-induced flow transport (RIFT) or/and transport by flow (FT) using a rainfall simulator and a 6 × 1 m² erosion plot and a silt loam. The results show a high degree of enrichment for size classes of 2–4 and 4–8 μm and a high degree of depletion for size classes of >63 μm under different slopes and rainfall intensities. In addition, the results show that the experimental enrichment ratio (ER) for particle size <16 μm under different slopes and rainfall intensities was greater than 1, while the ER for particle size >32 μm was less than 1.     

Bioconcentration and biomagnification of polybrominated diphenyl ethers (PBDEs) through lower-trophic-level coastal marine food web

Bivalves, crabs, fishes, seawater, and sediment collected from the inner part of Tokyo Bay, Japan, were measured for 20 polybrominated diphenyl ether (PBDE) and 5 polychlorinated biphenyl (PCB) congeners. To determine the trophic levels of the organisms, carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) were also measured. Bioconcentration factors of PBDE and PCB congeners increased as the octanol-water partition coefficient (K_ow) rose to log K_ow = 7, above which they decreased again. Biomagnification of PCBs and several PBDE congeners (BDE47, 99, 100, 153 and 154) up the trophic ladder was confirmed by a positive correlation between their concentrations and δ¹⁵N. Other PBDE congeners showed a negative or no correlation, suggesting their biotransformation through metabolism. The more hydrophobic congeners of both PBDEs (Br = 2-6) and PCBs (Cl = 6-9) were biomagnified more. It thus appears that PBDEs are less biomagnified than PCBs.     

Expression of Mammalian Metallothionein-I Gene in Cyanobacteria to Enhance Heavy Metal Resistance

Metallothionein (MT) from mammals is a low molecular weight (about 6–7 KD), and cystein-rich (20 cystein per molecular) protein (Vallee, 1991). So MT has the strong binding ability of metal such as Cd, Hg and Pd. Wild-typed cyanobacteria have their own metallothionein-like proteins, which are of low cysteine content and have weak ability to bind heavy metal. Therefore, it is imperative to transfer the MT-I gene from mammal into cyanobacteria cell for the absorption and accumulation of heavy metals in aqueous system including marine and lake ( Misra and Gedamu, 1989). We inserted the MT-I cDNA gene after the strong promoter PpsbA or Psmt into the intermediary vector pRL-439, and then pRL-MT was ligated with shuttle vector pKT-210 (a shuttle vector pDC-08 was used at an earlier time) to construct the shuttle expression vector pKT-MT. (The MT-I mutant -KKS- also was selected as aim gene.) Then the constructed vector was introduced into cyanobacterium Anabaena sp. PCC7120, Synechocystis sp. PCC6803 and Synechococcus sp. PCC7942 with triparental conjunctive transfer (Bryant, 1994). The expression efficiency is about 1%. We also used homologous recombination vector pTZ18-8 to introduce MT-I cDNA into chromosomes in cyanobacteria and got higher expression efficiency. Metal tolerance tests show that the transgenic cyanobacteria acquire metal resistance up to 60 μmol/g CdCl₂ and expression efficiency up to 1045 μg MT/g fresh cells according to the data of ELISA.     

REE and (э)Nd of clay fractions in sediments from the eastern Pacific Ocean: Evidence for clay sources

Clay fractions in the non-calcareous surface sediments from the eastern Pacific were analyzed for clay minerals, REE and 143Nd/144Nd. Montmorillonite/illite ratio (M/I ratio), total REE contents ((REE), LREE/HREE ratio and cerium anomaly (бCe) may effectively indicate the genesis of clay minerals. Clay fractions with M/I ratio >1, бCe (0.85, (REE (400 μg/g, LREE/HREE ratio (4, and REE patterns similar to those of pelagic sediments are terrigenous and autogenetic mixed clay fractions and contain more autogenetic montmorillonite. Clay fractions with M/I ratio <1, бCe=0.86 to 1.5, ΣREE=200 to 350 μg/g, LREE/HREE ratio (6 and REE distribution patterns similar to that of China loess are identified as terrigenous clay fraction. The 143Nd/144Nd ratios or (э)Nd values of clay fractions inherit the features of terrigenous sources of clay minerals. Clay fractions are divided into 4 types according to (э)Nd values. Terrigenous clay minerals of type I with the (э)Nd values of -8 to -6 originate mainly from North American fluvial deposits. Those of type II with the (э)Nd values of -9 to -7 are mainly from the East Asia and North American fluvial deposits. Those of type III with (э)Nd values of -6 to -3 could come from the central and eastern Pacific volcanic islands. Those of type IV with (э)Nd values of -13 to -12 may be from East Asia eolian. The terrigenous and autogenetic mixed clay fractions show patchy distributions, indicating that there are volcanic or hot-spot activities in the eastern Pacific plate, while the terrigenous clay fractions cover a large part of the study area, proving that the terrigenous clay minerals are dominant in the eastern Pacific.     

Intercalibration of international and domestic ~(40)Ar/~(39)Ar dating standards

40Ar/39Ar method is a high precision dating means, of which the age is obtained by contrasting the un- known sample with those of standards. Usually the age of standard is determined by K-Ar method in which the 38Ar spike should be added for measurement. However, the absolute concentration of 38Ar spike is measured through the calibrated standards in turn, al- though occasionally the concentration of 38Ar spike is determined by other dating methods, such as Rb-Sr, U-Pb methods, which is kn…     

Theoretical grain size limits for single-domain,pseudo-single-domain and multi-domain behavior in titanomagnetite (x = 0.6) as a function of low-temperature oxidation

A theoretical model of grain size variation of domain transitions in titanomagnetite (x = 0.6) as a function of oxidation (z) is presented. The superparamagnetic (SP) to single-domain (SD) transition d_s, the SD to two-domain (TD) transition d₀, the TD to three-domain (3D) transition and the pseudo-single domain (PSD) to multi-domain (MD) transition are calculated as a function of z. It is shown that all the transition grain sizes increase with z, except for the PSD-MD transition for z > 0.6. The calculations predict that d_s increases from 0.044 to 0.197 μm, d₀ increases from 0.54 to 13 μm, the TD-3D transition increases from 1.6 to 49 μm as z varies from 0 to 0.8. The PSD-MD transition increases from 42 μm at z = 0 to 150 μm at z = 0.6, whereas between z = 0.6 to z = 0.8, the PSD-MD transition decreases to 49 μm. Qualitatively, the model explains some of the trends in magnetic properties of submarine basalts with low-temperature oxidation. Quantitatively, the model does give reasonable estimates of the PSD-MD boundary and d₀, which are close to the experimental values for x = 0.6 and z = 0. Furthermore, the model predicts that psarks or two-domain grains could be the major contributors to the remanence of oxidized submarine pillow basalts.     

Persistent organic pollutants (POPs) in a small, herbivorous, arctic marine zooplankton (Calanus hyperboreus): trends from April to July and the influence of lipids and trophic transfer

Samples of Calanus hyperboreus, a herbivorous copepod, were collected (n = 20) between April and July 1998, and water samples (n = 6) were collected in May 1998, in the Northwater Polynya (NOW) to examine persistent organic pollutants (POPs) in a high Arctic marine zooplankton. Lipid content (dry weight) doubled, water content (r2 = 0.88) and delta15N (r2 = 0.54) significantly decreased, and delta13C significantly increased (r2 = 0.30) in the C. hyperboreus over the collection period allowing an examination of the role of these variables in POP dynamics in this small pelagic zooplankton. The rank and concentrations of POP groups in C. hyperboreus over the entire sampling was sum of PCB (30.1 +/- 4.03 ng/g, dry weight) > sum of HCH (11.8 +/- 3.23) > sum of DDT (4.74 +/- 0.74), sum of CHLOR (4.44 +/- 1.0) > sum of CIBz (2.42 +/- 0.18), although these rankings varied considerably over the summer. The alpha- and gamma-HCH and lower chlorinated PCB congeners were the most common POPs in C. hyperboreus. The relationship between bioconcentration factor (BCF) and octanol-water partition coefficient (Kow) observed for the C. hyperboreus was linear and near 1:1 (slope = 0.72) for POPs with a log Kow between 3 and 6 but curvilinear when hydrophobic POPs (log Kow > 6) were included. Concentrations of sum of HCH. Sum of CHLOR and sum of CIBz increased over the sampling period, but no change in sum of PCB or sum of DDT was observed. After removing the effects of time, the variables lipid content, water content, delta15N and delta13C did not describe POP concentrations in C. hyperboreus. These results suggest that hydrophobic POP (log Kow = 3.86.0) concentrations in zooplankton are likely to reflect water concentrations and that POPs do not biomagnify in C. hyperboreus or likely in other small, herbivorous zooplankton.     

Intercalibration of international and domestic 40Ar/39Ar dating standards

Four international standards, Ga1550, MMhb-1, Lp-6, Bem 4M, and one domestic standard BT-1 have been intercalibrated. The repeated measurements on MMhb-1 with different mass demonstrate that MMhb-1 is inhomogeneous in age and its average age is 519.8 Ma. The results of Bern 4M and Lp-6 reflect that they have an invariable value of ⁴⁰Ar*/³⁹Ar_k (F) and the ages we obtained are consensus with their K-Ar age: Lp-6=127.7Ma; Bern 4M=18.2 Ma. Analyses of BT-1 age spectra, Ca/K and Cl/K spectra as well as inverse isochrons indicate that the sample is homogeneous and invariable and keeps close chemically, with its trapped argon isotope composition close to the atmosphere. The dating results show that age values are reproducible and steady, total fusion age, step-heating age, plateau age and isochron age are in accord with each other within the error range (2σ). Therefore, we recommend 28.7 Ma as the calibrated age of BT-1. We also discuss the variation in neutron flux gradients of Beijing 49-2 reactor. It was found that the neutron flux gradient varies considerably, and more monitors (standard samples) are needed to fix the trend of variation. The coefficient of the 49-2 reactor that transfers the ratio of production rate of ³⁷Ar_Ca/³⁹Ar_K into Ca/K ratio is 1.78. This is different from that reported earlier, 2.0, which may be caused by the reconstruction of the reactor.     

A whole life cycle assessment on effects of waterborne PBDEs on gene expression profile along the brain-pituitary-gonad axis and in the liver of zebrafish

Polybrominated diphenyl ethers (PBDEs) are now found ubiquitously in the aquatic environment and biota, and there is a growing concern that PBDEs may disrupt endocrine systems, leading to reproductive impairments of aquatic animals. In our study, zebrafish (Danio rerio) were exposed to the 5 ng/L, 1 μg/L and 50 μg/L of DE-71 for the duration of the whole life cycle (120 days, from eggs to adults). The expression of selected genes along the brain-pituitary-gonadal (BPG) axis and liver, and the levels of plasma sex hormones were examined. In male fish, up-regulation of GnRH in brain, FSHβ and LHβ in pituitary, FSH-receptor, LH-receptor, and CYP19a in testis was clearly evident, while down-regulation of CYP11a and 3β-HSD was found in testis. In female fish, a 2.4-fold up-regulation of 3β-HSD was found in ovary upon exposure to 50 μg/L of DE-71. GnRH in brain, FSHβ and LHβ in pituitary were also up-regulated, while ERβ, TH and TPH in brain and GnRH-receptor in pituitary were significantly down-regulated. Hepatic ERα, AR and VTG in males were all down-regulated, while hepatic ERα and AR in female were up-regulated. Serum estradiol (E2) was reduced in both male and female upon exposure to DE-71, while significant increases in serum testosterone (T) and 11-keto-testosterone (11-KT) were only found in male but not female fish. The ratio of T/E2 as well as the ratio of 11-KT/E2 in male fish increased in a dose-dependent manner upon exposure to DE-71. Our overall results showed that whole life exposure of DE-71 altered the expression of regulatory genes and receptors at all three levels of the BPG axis in zebrafish, and the responses are sex dependent. The observed disruption of GnRH and GtHs can be further related to the subsequent disruption in both levels and balance sex steroid hormones.     

Accumulation of polychlorinated biphenyls (PCB) associated with bottom sediments in larvae of Chironomus riparius Meigen

Patterns of bioaccumulation of polychlorinated biphenyls (PCBs) by chironomid larvae (Chironomus riparius Meigen) were studied under laboratory conditions. Larvae were maintained for 20 days, separately in two batches of natural bottom sediments sampled from Rybinsk Reservoir (Russia), each differing in PCB content (425.6 μg / kg or 24.8 μg / kg dry weight, respectively). The study revealed that chironomid larvae accumulated PCBs at levels comparable to the PCB content measured in sediments from each exposure. The bioaccumulation coefficient (1.11 and 1.59, respectively, as per dry weight for compared sediment batches) depended directly on the sum PCB content in sediments. At high sediment PCB content, the ratios of homologous groups of PCBs in larvae and sediment were identical and corresponded to the Aroclor 1254 congeners profile; at lower PCB content, pronounced differences were revealed. In larvae, the ratios of 3, 4, 5, and 6CB homologues were evenly distributed at levels of 20–34 %, while the 4CB homologues prevailed (47 %) in sediments. The content of the latter compounds in larvae was lower than in sediments, and higher for the other homologous groups. The study indicates selective bioaccumulation of various homologous groups of PCBs under conditions of low sediment PCB content.     

Magma chambers beneath the Klyuchevskoy volcanic group (Kamchatka)

A 3D velocity model of the Earth’s crust beneath the Klyuchevskoy volcanic group has been constructed using the seismic tomography method. Anomalies of the velocity parameters related to the zones of magma supply to active volcanoes have been distinguished. Petrological data on the composition, temperature, and pressure of generation and crystallization of parental melts of Klyuchevskoy volcano magnesian basalts have been obtained. The parental melt corresponds to picrite (MgO = 13–14 wt %) with an ultimate saturation of SiO₂ (49–50 wt %), a high H₂O content (2.2–2.9%), and incompatible elements (Sr, Rb, Ba). This melt is formed at pressures of 15–20 kbar and temperatures of 1280–1320°C. Its further crystallization proceeds in intermediate magma chambers at two discrete pressure levels (i.e., greater than 6, and 1–2 kbar). The results of the petrological studies are in good agreement with the seismotomographic model.