Effect of combined pollution by heavy metals on soil enzymatic activities in areas polluted by tailings from Pb-Zn-Ag mine

Some enzymatic activities were determined in the areas polluted by tailings from Tiantai Pb-Zn-Ag Mine in Zhejiang Province of China. The results indicated the soil enzymatic activities decreased significantly with increase of concentrations of heavy metals or the distance away from mining tailing center, especially dehydrogenase and urease activities. Multivariate regression analysis between heavy metal contents and soil enzymatic activities indicated that single dehydrogenase activity was very significantly correlated to combined effect of soil heavy metals in mine area. Moreover, single urease, protease and acid phosphatase activities were significantly related to the combined effect of heavy metals. The results suggest it is feasible to use soil enzymatic activities to indicate the pollution situation by combined heavy metals in the soil of mine area.     

Spatial distribution of dissolved Pb, Hg, Cd, Cu and As in the Bohai Sea

Characteristics of the spatial distribution of selected dissolved heavy metals were analyzed during large scale surveys from August 12 to 25,2003 in the Bohai Sea.Dissolved Pb was the only element with average concentrations higher than the grade-one sea water quality standard of China.The spatial distribution of dissolved Pb in surface water was similar to those of Cd,Cu and As,where the isopleths generally indicated decreasing values from the bays to the central areas.Only for Hg did the high concentrations not only appear in Liaodong Bay,Bohai Bay and Laizhou Bay,but also in the Central Area,viz.not only in inshore but also in offshore areas. Vertical distributions of dissolved Pb,Cd,Cu and As were largely uniform,while that of dissolved Hg increased with depth.We infer that the input of pollutants from land was the main influencing factor for the detected distribution patterns of dissolved heavy metals, followed by the dynamics of sea water,release from bottom sediments and biochemical processes.Comparing with historical data, average concentrations of dissolved heavy metals appear to decline in recent years.     

Investigation of basic properties of fly ash from urban waste incinerators in China

Basic properties of fly ash samples from different urban waste combustion facilities in China were analyzed using as X-ray fluorescence （XRF）, scanning electron microscopy （SEM）, X-ray diffraction （XRD）. The leaching toxicity procedure and some factors influencing heavy metals distribution in fly ash were further investigated. Experimental results indicate that the fly ash structures are complex and its properties are variable. The results of XRF and SEM revealed that the major elements （〉10000 mg/kg, listed in decreasing order of abundance） in fly ash are O, Ca, Cl, Si, S, K, Na, Al, Fe and Zn. These elements account for 93% to 97%, and the content of Cl ranges from 6.93% to 29.18 %, while that of SiO2 does from 4.48% to 24.84%. The minor elements （1000 to 10000 mg/kg） include Cr, Cu and Pb. Primary heavy metals in fly ash include Zn, Pb, Cr, Cu etc. According to standard leaching test, heavy metal leaching levels vary from 0 to 163.10 mg/L （Pb） and from 0.049 to 164.90 mg/L （Zn）, mostly exceeding the Chinese Identification Standard for hazardous wastes. Morphology of fly ash is irregular, with both amorphous structures and polycrystalline aggregates. Further research showed that heavy metals were volatilized at a high furnace temperature, condensed when cooling down during the post-furnace system and captured at air pollution control systems. Generally, heavy metals are mainly present in the forms of aerosol particulates or tiny particulates enriched on surfaces of fly ash particles. The properties of fly ash are greatly influenced by the treatment capacities of incinerators or the variation of waste retention time in chamber. Fly ash from combustors of larger capacities generally has higher contents of volatile component and higher leaching toxicity, while those of smaller capacities often produce fly ash containing higher levels of nonvolatile components and has lower toxicity. The content of heavy metals and leaching toxicity maybe have no convincing correlation, and high alkali content of CaO greatly contribute to leaching toxicity of heavy metal and acid neutralization capacity against acid rain.     

Estimation of the accumulation rates and health risks of heavy metals in residential soils of three metropolitan cities in China

Heavy metal concentrations in urban soils are likely to increase over time because of continuous urbanization and heavy metal emissions. To estimate the accumulation rates of heavy metals in urban soils, we collected soil samples from residential areas with different building ages in the metropolitan cities of Shanghai, Shenzhen, and Beijing, China. Heavy metal concentrations in the soils varied among the cities and were primarily affected by soil parent material and the intensity of anthropogenic sources. Regression analyses revealed that the accumulation rates of Cd and Cu in the soils ranged from 0.0034 to 0.0039 mg/(kg•year) and 0.343 to 0.391 mg/(kg•year), respectively, and were similar across the three cities, while accumulation rates of Zn and Pb in Shanghai were higher than those in Shenzhen and Beijing. The higher accumulation rates of Zn and Pb in Shanghai can be explained by differences in city history and industrial structures among the cities. Residential soils with high health risks posed by the heavy metals were mostly collected from old towns of Shanghai because of high Pb content in the areas. Although recent urbanization resulted in elevated concentrations of Cd, Cu, Zn, and Pb in the residential soils, the effect on the total health risks of residents exposed to the soils was negligible.     

Distributions of typical contaminant species in urban short-term storm runoff and their fates during rain events： A case of Xiamen City

The pollutants in urban storm runoff,which lead to an non-point source contamination of water environment around cities,are of great concerns.The distributions of typical contaminants and the variations of their species in short term storm runoff from different land surfaces in Xiamen City were investigated.The concentrations of various contaminants,including organic matter,nutrients(i.e.,N and P) and heavy metals,were significantly higher in parking lot and road runoff than those in roof and lawn runoff.The early runoff samples from traffic road and parking lot contained much high total nitrogen(TN 6-19 mg/L) and total phosphorus(TP 1-3 mg/L).A large proportion(around 60%) of TN existed as total dissolved nitrogen(TDN) species in most runoff.The percentage of TDN and the percentage of total dissolved phosphorus remained relatively stable during the rain events and did not decrease as dramatically as TN and TP.In addition,only parking lot and road runoff were contaminated by heavy metals,and both Pb(25-120 μg/L) and Zn(0.1-1.2 mg/L) were major heavy metals contaminating both runoff.Soluble Pb and Zn were predominantly existed as labile complex species(50%-99%),which may be adsorbed onto the surfaces of suspended particles and could be easily released out when pH decreased.This would have the great impact to the environment.     

Effects of urbanization on heavy metal accumulation in surface soils, Beijing

Urbanization processes affect the accumulation of heavy metals in urban soils. Effects of urbanization on heavy metal accumulation in soils were studied using Beijing as an example. It has been suggested that the ecological function of vegetation covers shifting from natural to agricultural settings and then to urban greenbelts could increase the zinc(Zn) concentrations of soils successively. The Zn concentration of urban soils was significantly correlated to the percentage of the impervious land surface at the500 m × 500 m spatial scale. For urban parks, the age or years since the development accounted for 80% of the variances of cadmium(Cd) and Zn in soils. The population density,however, did not affect the heavy metal distributions in urban soils. To conclude, the urban age turned out to be a notable factor in quantifying heavy metal accumulation in urban soils.     

Variations in concentrations and bioavailability of heavy metals in rivers caused by water conservancy projects: Insights from water regulation of the Xiaolangdi Reservoir in the Yellow River

Water regulation of the Xiaolangdi Reservoir of the Yellow River was chosen as a case to investigate variations in concentrations and bioavailability of heavy metals caused by water conservancy projects in rivers. Water and suspended sediment (SPS) samples were collected at downstream sampling sites along the river during this period. Concentrations and speciation of Zn, Cr, Cu, Ni, and Pb in water and SPS samples were analyzed, and their bioaccumulation was studied with Daphnia magna. This study indicated that the exchangeable and carbonate-bound fractions of heavy metals in SPS decreased along the studied stretch, and the dissolved heavy metal concentrations increased along the river with 1.6–15 folds. This is because sediment resuspension increased along the river during water regulation, giving rise to the increase of heavy metal release from SPS. The dissolved Zn, Cu, Ni, and Pb concentrations were significantly positively correlated with SPS concentrations, and their increase along the river was greater than Cr. The body burdens of heavy metals in D. magna exposed into samples collected from the reservoir outlet were 1.3–3.0 times lower than those from downstream stations, suggesting that the heavy metal bioavailability increased during water regulation. This should be considered in the reservoir operation.     

Heavy metal availability and impact on activity of soil microorganisms along a Cu/Zn contamination gradient

All the regulations that define a maximum concentration of metals in the receiving soil are based on total soil metal concentration. However, the potential toxicity of a heavy metal in the soil depends on its speciation and availability. We studied the effects of heavy metal speciation and availability on soil microorganism activities along a Cu/Zn contamination gradient. Microbial biomass and enzyme activity of soil contaminated with both Cu and Zn were investigated. The results showed that microbial biomass was negatively affected by the elevated metal levels. The microbial biomass-C （Cmic）/organic C （Corg） ratio was closely correlated to heavy metal stress. There were negative correlations between soil microbial biomass, phosphatase activity and NH4NO3 extractable heavy metals. The soil microorganism activity could be predicted using empirical models with the availability of Cu and Zn. We observed that 72% of the variation in phosphatase activity could be explained by the NH4NO3-extractable and total heavy metal concentration. By considering different monitoring approaches and different viewpoints, this set of methods applied in this study seemed sensitive to site differences and contributed to a better understanding of the effects of heavy metals on the size and activity of microorganisms in soils. The data presented demonstrate the relationship between heavy metals availability and heavy metal toxicity to soil microorganism along a contamination gradient.     

Role of adsorption behavior on metal build-up in urban road dust

Metal pollution of stormwater runoff can cause potential toxic impacts on the receiving water environment and human health. Effective pollution mitigation requires accurate stormwater quality modeling. Even though a significant knowledge base exists on the factors influencing metal build-up on urban roads, very limited studies have investigated how metal–particulate interaction influences metal build-up. This study quantitatively assessed the influence of particulate characteristics, together with vehicular traffic and land use, on the build-up of Zn, Cu, Pb, Cr, Ni and Cd on urban roads. The study outcomes revealed that the variability in metal build-up is highly influenced by the variability associated with metal adsorption to particulates. The percentage contribution from particulate properties influencing metal adsorption in the case of 150 μm size road dust particles was found to be higher(Zn 44%, Cu 52%, Cr 16%, Ni 27% and Cd 45%) when compared to traffic and land use characteristics(Zn 21%, Cu 13%, Cr and Ni 10% and Cd 34%). Similar adsorption behavior was noted for metals associated with 150 μm size road dust particles. Among different particulate properties influencing metal adsorption, effective cation exchange capacity showed a strong positive relationship with the build-up of Cd compared to other metals,highlighting the potential role of Cd in stormwater quality as a readily available metal. The build-up of metals such as Cr and Ni are highly influenced by metal oxides of Al, Fe and Mn and clay forming minerals, indicating that Cr and Ni are relatively stable in nature.     

Limitation of spatial distribution of ammonia-oxidizing microorganisms in the Haihe River, China, by heavy metals

The Haihe River is characterized by high ammonia pollution. Therefore, it is necessary to determine how environmental factors, such as heavy metals in the river limit the spatial distribution of ammonia-oxidizing microorganisms. In this study, the relationships between five heavy metals and ammonia-oxidizing microorganisms were studied. The results showed that under high ammonia, low oxygen and high concentrations of suspended particles, ammonia-oxidizing bacteria(AOB) ranged from 101:3 to 104:8 gene copies/mL and ammonia-oxidizing archaea(AOA) ranged from 102:7 to 104:9 gene copies/mL. The average metal concentrations in water were 23.57(Cr), 21.58(Ni), 65.09(Cu), 622.03(Zn) and 10.16(As) μg/L, with those of Zn, Cu and Cr being higher than the US EPA criteria. Scatter plots of microbial abundance and metals indicated that both AOA and AOB were limited by heavy metals, but in different ways. As had an inhibitory effect on AOB, while Ni and Zn promoted AOA, and the other metals investigated showed no significant correlation with microbial abundance. Overall, our results indicated that the effects of heavy metals on ammonia-oxidizing microorganisms in water are complex, and that the final effect is determined by the physiological role of each element in the microorganisms, as well as environmental conditions such as complexation of organic matter, not simply the total metal concentration.     

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.