Sequence, biochemical characteristics and expression of a novel Sigma-class of glutathione S-transferase from the intertidal copepod, Tigriopus japonicus with a possible role in antioxidant defense

Glutathione S-transferases (GSTs) play a major role in detoxification of xenobiotics and antioxidant defense. Here we report full-length cDNA sequence of a novel Sigma-class of GST (GST-S) from the intertidal copepod Tigriopus japonicus. The full sequence was of 1,136 bp in length containing an open reading frame (ORF) of 651 bp that encoded 217 amino acid residues. The recombinant Tigriopus GST-S was highly expressed in transformed Escherichia coli. Kinetic properties and effects of pH, temperature and chemical inhibitors on Tigriopus GST-S were also studied. The expression of GST-S was studied using real-time RT-PCR in response to exposure to two oxidative stresses-inducing agents, viz., hydrogen peroxide (H(2)O(2)) and heavy metals (copper, manganese). It was observed that H(2)O(2) (2mM) exposure down-regulated its expression at the initial stage but there was recovery and up-regulation shortly afterwards. In case of heavy metal exposure there was concentration-dependent increase in Tigriopus GST-S gene expression up to 24h. These results suggest that Tigriopus GST-S expression is modulated by prooxidant chemicals and it may play a role against oxidative stress. A majority of other GST isoforms is known to play an important role in antioxidant defense. This study provides a preliminary insight into the possible antioxidant role for Sigma-class of GST in T. japonicus.     

Bio-reduction of N-nitrosodimethylamine (NDMA) using a hydrogen-based membrane biofilm reactor

N-Nitrosodimethylamine (NDMA) is a disinfection by-product shown to be carcinogenic, mutagenic, and teratogenic. A feasible detoxification pathway for NDMA is a three-step bio-reduction that leads to ammonia and dimethylamine. This study examines the bio-reduction of NDMA in a H2-based membrane biofilm reactor (MBfR) that also is active in nitrate and sulfate reductions. In particular, the study investigates the effects of H2 availability and the relative loadings of NDMA, nitrate, and sulfate, which potentially are competing electron acceptors. The results demonstrate that NDMA was bio-reduced to a major extent (i.e., at least 96%) in a H2-based MBfR in which the electron-equivalent fluxes from H2 oxidation were dominated by nitrate and sulfate reductions. NDMA reduction kinetics responded to NDMA concentration, H2 pressure, and the presence of competing acceptors. The most important factor controlling NDMA-reduction kinetics was the H2 availability, controlled primarily by the H2 pressure, and secondarily by competition from nitrate reduction.     

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.     

Survey of coastal inland pollution sources and their influence on seawater quality in Doam bay,Korea

Inland pollution sources of Doam bay were investigated from August to October in 2013. A total of 210 sources including rivers, streams, domestic, agricultural and industrial discharge points were identified along the coast, including 32 sources that had outflow. Agricultural sources were the largest inland pollution sources (139, 66.2%). Fecal coliform concentrations were measured. These data were combined with water discharge data to determine daily loads of pollutants discharged from each source into the bay. Fecal coliform concentrations were the highest in domestic discharges. However, they only had slight influence because their discharge volume was small. The most significant pollution source was Tamjin River (St.85) due to large amount of discharge volume. The influence of St.85 reached almost half of Doam bay. Fecal coliform levels of streams increased after rainfall, but decreased overtime. Domestic pollution sources were not affected upon rain event.     

Geochemical occurrences of arsenic and fluoride in bedrock groundwater: a case study in Geumsan County,Korea

Bedrock groundwaters in Geumsan County, Korea, were surveyed to investigate the distribution and geochemical behaviors of arsenic and fluoride, mobilized through geogenic processes. The concentrations were enriched up to 113 μg/L for arsenic and 7.54 mg/L for fluoride, and 16% of 150 samples exceeded World Health Organization drinking water guidelines for each element. Simple Ca-HCO₃ groundwater types and positive correlations with pH, Ca, SO₄, and HCO₃ were characteristics of high (>10 μg/L) As groundwaters. The oxidation reaction of sulfide minerals in metasedimentary rocks and locally mineralized zones seems to be ultimately responsible for the existence of arsenic in groundwater. Desorption process under high pH conditions may also control the arsenic mobility in the study area. High (>1.5 mg/L) F groundwaters were found in the Na-HCO₃ type and with greater depth. Fluoride seemed to be enriched by deep groundwater interaction with granitic rocks, and continuous supply to shallow Ca-HCO₃-type groundwater kept the concentration high. In the study area, drinking water management should include periodic As and F monitoring in groundwater.

     

GROUND WATER DROUGHT MANAGEMENT BY A FEEDFORWARD CONTROL METHOD1

ABSTRACT: Management of a regional ground water system to mitigate drought problems at the multi‐layered aquifer system in Collier County, Florida, is the main topic. This paper developed a feedforward control system that consists of system and control equations. The system equation, which forecasts ground water levels using the current measurements, was built based on the Kalman filter algorithm associated with a stochastic time series model. The role of the control equation is to estimate the pumping reduction rate during an anticipated drought. The control equation was built based on the empirical relationship between the change in ground water levels and the corresponding pumping requirement. The control system starts with forecasting one‐month‐ahead ground water head at each control point. The forecasted head is in turn used to calculate the deviation of ground water heads from the monthly target specified by a 2‐in‐10‐year frequency. When the forecasted water level is lower than the target, the control system computes spatially‐varied pumping reduction rates as a recommendation for ground water users. The proposed control system was tested using hypothetical droughts. The simulation result revealed that the estimated pumping reduction rates are highly variable in space, strongly supporting the idea of spatial forecasting and controlling of ground water levels as opposed to a lumped water use restriction method used previously in the model area.     

Blood levels of cadmium and lead in residents near abandoned metal mine areas in Korea

We analyzed national data on blood lead levels (BLL) and blood cadmium levels (BCL) in residents living near 38 abandoned metal mining areas (n?=?5,682, 18–96 years old) in Korea that were collected by the first Health Effect Surveillance for Residents in Abandoned Metal mines (HESRAM) from 2008 to 2011. The geometric mean BCL and BLL were 1.60 μg/L (95 % CI?=?1.57–1.62 μg/L) and 2.87 μg/dL (95 % CI?=?2.84–2.90 μg/dL), respectively, notably higher than levels in the general population in Korea and other countries. We found significantly higher BLL and BCL levels in people living within 2 km of an abandoned metal mine (n?=?3,165, BCL?=?1.87 μg/L, BLL?=?2.91 μg/dL) compared to people living more than 2 km away (n?=?2,517, BCL?=?1.31 μg/L, BLL?=?2.82 μg/dL; P?<?0.0001) and to the general population values reported in the literature.     

Birnessite mediated debromination of decabromodiphenyl ether

Decabromodiphenyl ether (BDE-209) is a major component of a commercial flame retardant formulation; however, there is limited information on the fate of BDE-209 in the environment, including metal oxide mediated degradation. Laboratory experiments were conducted to investigate the birnessite (delta-MnO(2))-promoted debromination of BDE-209 in tetrahydrofuran (THF)-water systems as well as catechol solutions. Up to 100% (0.1044 micromol initial charge) of BDE-209 disappeared upon reaction with birnessite in THF/H(2)O (4:6-9:1). The formation of aqueous Br(-) from BDE-209 reduction was determined and up to 16 mole% of initial bromine was released over the course of the reaction indicating approximately 1.7 Br-C bonds were reduced per BDE-209 molecule. The distribution of debrominated congeners, however, indicated a much greater extent of debromination for some products than what was inferred from an average bromine mass balance. The produced congeners varied from tetra- to nona-bromodiphenyl ether, including BDE-47 and -99, during the 24 h reaction. Experiments with deuterated water indicated that water was not the major hydrogen donor in the reduction but rather THF provided the reducing power. This conclusion was supported by the presence of succinic acid, which was produced from oxidation of THF. The reactions with aqueous catechol, rather than THF-water mixtures, were performed to assess the possible role that compounds found in natural environments, such a tannin-like phenols, might have on the chemistry. These experiments indicated that birnessite mediated debromination of BDE-209 might occur in natural settings.