Arsenic speciation in fish from Greek coastal areas

Arsenic speciation analysis was conducted on fish samples(sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf,Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to62.6 mg As/kg dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8 mg As/kg dry weight, accounting for67–95% of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072–0.956 mg As/kg dry weight.Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity,total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, are potentially correlated to As species concentrations. Furthermore, based on factor analysis, the biological parameters, such as fish weight, lipids, protein and ash content,that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated.     

The potential risk assessment for different arsenic species in the aquatic environment

The different toxicity characteristics of arsenic species result in discrepant ecological risk.The predicted no-effect concentrations(PNECs) 43.65, 250.18, and 2.00 × 103μg/L were calculated for As(III), As(V), and dimethylarsinic acid in aqueous phase, respectively. With these PNECs, the ecological risk from arsenic species in Pearl River Delta in China and Kwabrafo stream in Ghana was evaluated. It was found that the risk from As(III) and As(V)in the samples from Pearl River Delta was low, while much high in Kwabrafo stream. This study implies that ecological risk of arsenic should be evaluated basing on its species.     

The potential risk assessment for different arsenic species in the aquatic environment

The different toxicity characteristics of arsenic species result in discrepant ecological risk. The predicted no-effect concentrations (PNECs) 43.65, 250.18, and 2.00 × 10³ μg/L were calculated for As(III), As(V), and dimethylarsinic acid in aqueous phase, respectively. With these PNECs, the ecological risk from arsenic species in Pearl River Delta in China and Kwabrafo stream in Ghana was evaluated. It was found that the risk from As(III) and As(V) in the samples from Pearl River Delta was low, while much high in Kwabrafo stream. This study implies that ecological risk of arsenic should be evaluated basing on its species.     

Effects of simulated acid rain on root growth of Cunninghamia lanceolata and Schima superba saplings planted in acidified soil

Results from pot culture (with one-year old Cunninghamia lanceolata and Schima superba) are described. It was found that the biomass production and elongation of C. lanceolata was seriously inhibited at pH 2.0 rain, but for S. superba, was not affected markedly. When pH values of experimental rain were higher than 2.0, the root growth of both species was not adversely affected. Aluminium had already accumulated to some degrees in the roots of both trees, and started to affect the root growth of C. lanceolata at pH 2.0 rain. The soil chemistry was also examined. Increased acidity of experimental rain increased the leaching of Ca and Mg. The Al/Ca mol ratio increased from 0.3 to 0.9 in top soil, and in rhizosphere to 1.5 when the pH values of simulated acid rain were 4.5 to 2.0. In this experiment, NO3- fertilization effect was discovered.     

Arsenic species in electronic cigarettes: Determination and potential health risk

Human exposure to contaminants from electronic cigarettes(e-cigarettes) and the associated health effects are poorly understood.There has been no report on the speciation of arsenic in e-liquid(solution used for e-cigarettes) and aerosols.We report here determination of arsenic species in e-liquids and aerosols generated from vaping the e-liquid.Seventeen e-liquid samples of major brands,purchased from local and online stores in Canada and China,were analyzed for arsenic species using high-performance liquid chromatography and inductively coupled plasma mass spectrometry.Aerosols condensed from vaping the eliquids were also analyzed and compared for arsenic species.Six arsenic species were detected,including inorganic arsenate(iAs~Ⅴ),arsenite(iAs~Ⅲ),monomethylarsonic acid(MMA),and three new arsenic species not reported previously.In e-liquids,iAs~Ⅲ was detected in 59%,iAs~Ⅴ in 94%,and MMA in 47% of the samples.In the condensate of aerosols from vaping the e-liquids,iAs~Ⅲ was detected in 100%,iAsv in 88%,and MMA in 13% of the samples.Inorganic arsenic species were predominant in e-liquids and aerosols of e-cigarettes.The concentration of iAs~Ⅲ in the condensate of aerosols(median 3.27 μg/kg) was significantly higher than that in the e-liquid(median 1.08 μg/kg) samples.The concentration of inorganic arsenic in the vaping air was approximately 3.4 μg/m~3,which approaches to the permissible exposure limit(10 μg/m~3) set by the United States Occupational Safety and Health Administration(OSHA).According to the Environmental Protection Agency's unit risk factor(4.3 × 10~(-3) per μg/m~3) for inhalation exposure to inorganic arsenic in the air,the estimated excess lung cancer risk from lifetime exposure to inorganic arsenic in the ecigarette vaping air(3.4 μg/m~3),assuming e-cigarette vaping at 1% of the time,is as high as1.5 × 10~(-4).These results raise health concerns over the exposure to arsenic from electronic cigarettes.     

Determination of arsenic in air particulates and diesel exhaust particulates by spectrophotometry

A method was developed for the determination of trace arsenic by spectrophotometry. The proposed method is rapid, simple,and inexpensive. This method can be used for sensitive determination of trace arsenic in environmental samples and especially in air particulates. The results obtained by this method as a proposed method were compared with those obtained by hydride generation atomic absorption spectrometry as a popular reported method for the determination of arsenic and an excellent agreement was found between them. The method was also used for determination of arsenic associated with airborne particulate matter and diesel exhaust particulates.The results showed that considerable amount of arsenic are associated with diesel engine particulates. The variation in concentration of arsenic was also investigated. The atmospheric concentration of arsenic was different in different sampling stations was dependent to the traffic density.     

Evaluation of antioxidant enzymes activities and identification of intermediate products during phytoremediation of an anionic dye (C. I. Acid Blue 92) by pennywort (Hydrocotyle vulgaris)

The potential of pennywort(Hydrocotyle vulgaris)for phytoremediation of C.I.Acid Blue 92(AB92)was evaluated.The efects of various experimental parameters including pH,temperature,dye concentration and plant weight on dye removal efciency were investigated.The results showed that the optimal condition for dye removal were pH 3.5 and temperature 25°C.Moreover,the absolute dye removal enhanced with increase in the initial dye concentration and plant weight.Pennywort showed the same removal efciency in repeated experiments(four runs)as that obtained from the first run(a 6-day period).Therefore,the ability of the plant in consecutive removal of AB92 confirmed the biodegradation process.Accordingly,a number of produced intermediate compounds were identified.The efect of treatment on photosynthesis and antioxidant defense system including superoxide dismutase,peroxidase and catalase in plant roots and leaves were evaluated.The results revealed a reduction in photosynthetic pigments content under dye treatments.Antioxidant enzyme responses showed marked variations with respect to the plant organ and dye concentration in the liquid medium.Overall,the increase in antioxidant enzyme activity under AB92 stress in the roots was much higher than that in the leaves.Nevertheless,no significant increase in malondialdehyde content was detected in roots or leaves,implying that the high efciency of antioxidant system in the elimination of reactive oxygen species.Based on these results,pennywort was founded to be a capable species for phytoremediation of AB92-contaminated water,may be efective for phytoremediation dye-contaminated polluted aquatic ecosystems.     

Phylogenetic analysis and arsenate reduction e ect of the arsenic-reducing bacteria enriched from contaminated soils at an abandoned smelter site

Microbial reduction of As(V) (i.e., arsenate) plays an important role in arsenic (As) mobilization in aqueous environment. In this study, we investigated As(Ⅴ) reduction characteristics of the bacteria enriched from the arsenic-contaminated soil at an abandoned smelter site. It was found that As(Ⅴ) was completely reduced to As(Ⅲ) (i.e., arsenite) in 21 h. After 3-d incubation, a yellow solid was precipitated and the concentration of As(Ⅲ) decreased sharply. After 150 h incubation, ca. 65% of soluble arsenic was removed from the solution. The analysis of the precipitate by scanning electron microscopy and energy dispersive spectrometer (SEM-EDS) and X-ray diffraction (XRD) revealed that the main component was crystalline arsenic sulfide (ASS). Microbial mediated reduction and mobilization of adsorbed As(Ⅴ) on ferric hydroxide was also examined. In the microcosm slurry experiment, ca. 53% of the adsorbed As(V) was reduced to As(Ⅲ) by the bacteria, which resulted in an appreciable release of arsenic into aqueous phase. The released arsenic was present predominantly as As(Ⅲ). The microbial diversity was analyzed by 16S rDNA-dependent molecular phylogeny. A near-full-length 16S rDNA gene clone library was constructed. The 197 clones were analyzed using RFLP (restriction fragment length polymorphism) and 72 OTUs were obtained, which contributed 51% of the content for total clone number in six OTUs. Six bacterial clones in these six OTUs were selected for sequencing and the sequenced clones were found to belong to the group Caloramator, Clostridium, and Bacillus.     

Effects of litter removal on plant species diversity: a case study in tropical Eucalyptus forest ecosystems in South China

The removal of litterfall in the Eucalyptus plantations in South China affected the plant biodiversity in these ecosystems was found based on the field observation and lab analysis.The protection times of species diversity of three Eucalyptus communities were different (Community Ⅰ with no protection,Community Ⅱ with 7-year-protection,Community Ⅲ with 35-year-protection).The total numbers of species in these communities(from Community Ⅰ to Ⅱ to Ⅲ)are 1,6,and 17,respectively.The tesults showed that the protection of litterfall from being taken out of the ecosystem is important and can increase plant species diversity.This study ombined biomass data,the chemical and physical properties of the soil,and the diversity of microbes in the communities.It is concluded that the mechanism of the effects of litter removal on biodiversity includes three factors:removing the suitable habitat of microbe and animal,decreasing the soil mutrient, and changing the special habitat for the germination and growth of invading plants.These results should have important implications for managing these Eucalyptus forest ecosystems in South China.     

Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds (VOSCs): methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and dimethyl tetrasulfide (DMTeS). Even in the untreated control without a methionine addition, methionine and its catabolites (VOSCs, mainly DMDS) were found in considerable amounts that were high enough to account for the water’s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine+glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.