Mineralization and kinetics of Reactive Brilliant Red X-3B by a combined anaerobic-aerobic bioprocess inoculated with the coculture of fungus and bacterium.

Mineralization of Reactive Brilliant Red X-3B by a combined anaerobic-aerobic process which was inoculated with the co-culture of Penicillium sp. QQ and Exiguobacterium sp. TL was studied. The optimal conditions of decolorization were investigated by response surface methodology as follows: 132.67 g/L of strain QQ wet spores, 1.09 g/L of strain TL wet cells, 2.25 g/L of glucose, 2.10 g/L of yeast extract, the initial dye concentration of 235.14 mg/L, pH 6.5, and 33 °C. The maximal decolorization rate was about 96 % within 12 h under the above conditions. According to the Haldane kinetic equation, the maximal specific decolorization rate was 89.629 mg/g˙h. It was suggested that in the anaerobic-aerobic combined process, decolorization occurred in the anaerobic unit and chemical oxygen demand (COD) was mainly removed in the aerobic one. Inoculation of fungus QQ in the anaerobic unit was important for mineralization of X-3B. Besides, the divided anaerobic-aerobic process showed better performance of COD removal than the integrated one. It was suggested that the combined anaerobic-aerobic process which was inoculated with co-culture was potentially useful for the field application.

Dynamics of three organic acids (malic, acetic and succinic acid) in sunflower exposed to cadmium and lead.

Sunflower (Helianthus annuus L.) has been considered as a good candidate for bioaccumulation of heavy metals. In the present study, sunflower was used to enrich the cadmium and lead in sand culture during 90 days. Biomass, Cd and Pb uptake, three organic acids and pH in cultures were investigated. Results showed that the existence of Cd and Pb showed different interactions on the organic acids exudation. In single Cd treatments, malic and acetic acids in Cd10 showed an incremental tendency with time. In the mixed treatments of Cd and Pb, malic acids increased when 10 and 40 mg x L(-1) Cd were added into Pb50, but acetic acids in Pb50 were inhibited by Cd addition. The Cd10 supplied in Pb10 stimulated the secretion of malic and succinic acids. Moreover, the Cd or Pb uptake in sunflower showed various correlations with pH and some organic acids, which might be due to the fact that the Cd and Pb interfere with the organic acids secretion in rhizosphere of sunflower, and the changes of organic acids altered the form and bioavailability of Cd and Pb in cultures conversely.

Biotransformation of chloro-substituted indoles to indigoids by phenol hydroxylase from Arthrobacter sp. W1.

Recombinant Escherichia coli cells expressing phenol hydroxylase (designated as strain PH(IND)) were used to synthesize chloro-substituted indigoids by the transformation of indoles. The optimal conditions for the biotransformation of 4- and 7-chloroindole were determined by response surface methodology. Biotransformation kinetic assays revealed that strain PH(IND) showed high catalytic efficiency for 4- and 7-chloroindole. The formation rate of 7,7'-dichloroindigo (1.35 unit/mg cell dry weight) by strain PH(IND) was 1.14-fold higher than that of 4,4'-dichloroindigo. The intermediates of 7-chloroindole biotransformation were identified by high-performance liquid chromatography-mass spectroscopy, and the biotransformation mechanism was also proposed. These results suggested that there was a potential application of strain PH(IND) in the biotransformation of chloro-substituted indoles to valuable indigoids.

Effects of bacteria on cadmium bioaccumulation in the cadmium hyperaccumulator plant Beta vulgaris var. cicla L.

To investigate the effects of two cadmium-tolerant bacteria, Staphylococcus pasteuri (S. pasteuri X1) and Agrobacterium tumefaciens (A. tumefaciens X2), on cadmium uptake by the cadmium hyperaccumulator plant Beta vulgaris var. cicla L., a pot experiment with artificially contaminated soil was conducted. The results demonstrated that both cadmium-tolerant bacteria enhanced the dry weight of Beta vulgaris var. cicla L. The total dry weights of plants in the control CK20, S. pasteuri X1 and A. tumefaciens X2 treatments were 0.85, 1.13, and 1.38 g/pot, respectively. Compared with the control CK20 findings, the total dry weight of plants was increased by 32.8 and 61.1% after inoculation with S. pasteuri X1 and A. tumefaciens X2, respectively, indicating that A. tumefaciens X2 more strongly promoted the growth of Beta vulgaris var. cicla L. than S. pasteuri X1. In addition, inoculation with S. pasteuri X1 and A. tumefaciens X2 significantly (p < 0.05) promoted cadmium uptake by plants and improved the bioaccumulation of cadmium by the plants from the soil. Moreover, the inoculation of S. pasteuri X1 and A. tumefaciens X2 effectively facilitated the transfer of cadmium in the soil from the Fe-Mn oxide and residual fractions to the soluble plus exchangeable and weakly specially adsorbed fractions in the rhizosphere soils of plants. The bacterial enhancement of cadmium phytoavailability might provide a potential and promising method to increase the efficiency of phytoextraction.

Biotransformation of indole to indigo by the whole cells of phenol hydroxylase engineered strain in biphasic systems.

Biotransformation of indole to indigo in liquid-liquid biphasic systems was performed in Escherichia coli cells expressing phenol hydroxylase. It was suggested that indole could inhibit the cell growth even at low concentration of 0.1 g/L. The critical Log P for strain PH_(IND) was about 5.0. Three different solvents, i.e., decane, dodecane, and dioctyl phthalate, were selected as organic phase in biphasic media. The results showed that dodecane gave the highest yield of indigo (176.4 mg/L), which was more than that of single phase (90.5 mg/L). The optimal conditions for biotransformation evaluated by response surface methodology were as follows: 540.26 mg/L of indole concentration, 42.27 % of organic phase ratio, and 200 r/min of stirrer speed; under these conditions, the maximal production of indigo was 243.51 mg/L. This study proved that the potential application of strain PH_(IND) in the biotransformation of indole to indigo using liquid-liquid biphasic systems.

Spatial distribution and seasonal variation of polycyclic aromatic hydrocarbons (PAHs) contaminations in surface water from the Hun River, Northeast China.

The objectives of this study were to investigate the levels, dispersion patterns, seasonal variation, and sources of 16 priority polycyclic aromatic hydrocarbons (16 EPA-PAHs) in the Hun River of Liaoning Province, China. Samples of surface water were collected from upstream to downstream locations, and also from the main tributaries of the Hun River in dry period, flood period, and level period, respectively. After appropriate preparation, all samples were analyzed for 16 EPA-PAHs. Total PAHs concentrations varied from 124.55 to 439.27 ng l(-1) in surface water in dry period, 1,615.75 to 5,270.04 ng l(-1) in flood period, and 2,247.42 to 7,767.9 ng l(-1) in level period. The 16 EPA-PAHs concentrations were significantly increased in the order of level period > flood period > dry period. The composition pattern of PAHs in surface water was dominated by low molecular weight PAHs, in particular two- to three-ring PAHs. In addition, two-ring PAH accounted for 39.33 to 88.27 % of the total PAHs in level period. Low molecular weight PAHs predomination together with higher levels of PAHs in flood and level period suggested a relatively recent local source of PAHs. Special PAHs ratios such as phenanthrene/anthracene and fluoranthene/pyrene indicated that under dry weather season conditions, the PAHs found in surface water were primarily from petrogenic source, while under wet weather season conditions they were from mixed source of both petrogenic inputs and combustion sources. The comparison of PAHs contamination among different types of areas in China suggested that atmospheric depositions might be the most important approaches of PAHs into water system. Although the Hun River exists low PAHs ecological risk now, potential toxic effects will be existed in the future especially in flood and level period.

Biotransformation of benzene and toluene to catechols by phenol hydroxylase from Arthrobacter sp. W1.

Phenol hydroxylase gene engineered microorganism (PHIND) was used to synthesize catechols from benzene and toluene by successive hydroxylation reaction. HPLC-MS and (1)H NMR analysis proved that the products of biotransformation were the corresponding catechols via the intermediate production of phenols. It was indicated that the main products of toluene oxidation were o-cresol and p-cresol. 3-Methylcatechol was the predominant product for m-cresol biotransformation. Formation rate of catechol (25 µM/min/g cell dry weight) was 1.43-fold higher than that of methylcatechols. It was suggested that phenol hydroxylase could be successfully used to transform both benzene and toluene to catechols by successive hydroxylation.

Comparison of the treatment performance of bio-substrate based and meadow brown soil based subsurface infiltration systems for domestic wastewater treatment.

To foster the practical development of subsurface wastewater infiltration (SWI) systems in China, two systems were implemented on the campus of Shenyang University. The bio-substrate filled SWI (BSWI) and meadow brown soil filled SWI (MSWI) system operated under the same operation mode. According to the 12-month experimental results, the bio-substrate had much higher potential to be a good substrate as compared to the meadow brown soil. The maximum adsorbing capability for NH(4)(+)-N of the bio-substrate was 0.724 mg/g, while for the meadow brown soil, the maximum value was 0.471 mg/g. The amounts of nitrifying and denitrifying bacteria of the BSWI were one order of magnitude higher than that for the MSWI. Ammonia, nitrite and nitrate nitrogen concentrations implied nitrification-denitrification process went well in the BSWI. Moreover, the BSWI system maintained efficient pollutants removal, the mean removal efficiencies were 92.3 ± 1.5%, 96.5 ± 3.1%, 90.0 ± 2.1%, 78.6 ± 1.2%, 91.2 ± 1.1% and 99.7 ± 1.0% for COD, BOD(5), NH(4)(+)-N, TN, TP and SS, respectively. As compared with the MSWI system, pollutant removal efficiencies improved by 26.8 ± 2.3% for NH(4)(+)-N, 33.8 ± 1.7% for TN, 22.4 ± 1.4% for COD, 26.0 ± 3.5% for BOD(5) and 14.7 ± 2.9% for TP, respectively.

Adsorption and catalytic hydrolysis of carbaryl and atrazine on pig manure-derived biochars: impact of structural properties of biochars.

Biochars were produced from pig manure to elucidate the influence of biochars with high ash contents on the fate of pesticides. Adsorption and catalytic hydrolysis of carbaryl and atrazine on original biochars and deashed biochars were investigated. The two pesticides were substantially adsorbed by the biochars, with organic carbon normalized sorption coefficient (K(oc)) values of 10(2.65)-10(3.66) L/kg for carbaryl and 10(1.90)-10(3.57) L/kg for atrazine at C(e) of 0.5 mg/L. Hydrophobic effect alone could not explain the sorption, and several other processes including pore-filling and π-π electron donor-acceptor interactions were involved in pesticide adsorption. Adsorption increased greatly on the deashed biochar, indicating that some organic sorption sites in the original biochars were blocked or difficult to access due to their interactions with inorganic moiety. The pesticides were found to hydrolyze faster in the presence of biochars, and in the presence of biochar pyrolyzed at 700 °C, carbaryl and atrazine were decomposed by 71.8% and 27.9% in 12 h, respectively. The elevated solution pH was the main reason for the enhanced hydrolysis; however both the mineral surface and dissolved metal ions released from the biochars were confirmed to catalyze the hydrolysis.

Remediation of cadmium-contaminated soil by extraction with para-sulphonato-thiacalix[4]arene, a novel supramolecular receptor.

Batch extractions were conducted to evaluate the performance of para-sulphonato-thiacalix[4]arene (STC[4]A), a novel supramolecular receptor, for removing cadmium (Cd) from soil. The extraction mechanism was investigated by determination of the conditional stability constants (log K) of the STC[4]A-Cd complex. The influences of various variables were examined, including pH, contact time, and extractant concentration. The Cd extraction efficiency increased with increasing pH, reaching the maximum at pH 11 and then declining at higher pH values. This pH dependence was explained by the variation in the log K value of the STC[4]A-Cd complex along with pH change. When the STC[4]A dose was increased to an STC[4]A:Cd molar ratio of 2.5:1, Cd was exhaustively removed (up to 96.8%). The comparison experiment revealed that the Cd extraction performance of STC[4]A was almost equivalent to that of EDTA and significantly better than that of natural organic acids. STC[4]A extraction could efficiently prevent co-dissolution of soil minerals.

Performance evaluation of subsurface wastewater infiltration system in treating domestic sewage.

This study was to investigate domestic treatment efficiency of a subsurface wastewater infiltration (SWI) system over time. The performances of a young SWI system (in Shenyang University, China, fully operated for one year) and a mature SWI system (in Shenyang Normal University, China, fully operated for seven years) under the same operation mode were contrasted through field-scale experiments for one year. The performance assessment for these systems is based on physical and chemical parameters collected. The removal efficiencies within the young system were relatively high if compared with the mature one: for biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS), ammonia nitrogen (NH(3)-N) and total phosphorus (TP) were 95.0, 89.1, 98.1, 87.6 and 98.4%, respectively. However, the removal efficiencies decreased over time. The mean removal efficiencies for the mature SWI system were as follows: BOD (89.6%), COD (87.2%), SS (82.6%), NH(3)-N (69.1%) and TP (74.4%). The results indicate that the mature SWI system successfully removed traditional pollutants such as BOD from domestic wastewater. However, the nutrient reduction efficiencies (including NH(3)-N and TP) decreased after seven years of operation of the mature SWI system. Meanwhile, the SWI system did not decrease the receiving surface water quality.

Leaching of heavy metals from artificial soils composed of sewage sludge and fly ash.

The purpose of this study was to determine the leaching characteristics of heavy metals from artificial soils composed of sewage sludge and fly ash. A leaching experiment was carried out over a period of 90 days. The leachates from artificial soils were collected every 15 days, and the concentrations of cadmium, lead, copper, zinc, chromium, and nickel in leachates were determined. Results showed that pH values of the artificial soils leachate were stable, ranging from 6.71 to 7.62 at the end of the experiment. Except of the cadmium, the concentrations of chromium, nickel, and copper in leachates of the artificial soils reached a stable level at the end of the experiment. The final concentrations of copper in leachates varied from 27.1 to 127.5 µg L(-1), which was lower than European threshold value for drinking water, (1,000 µg L(-1)), while final nickel and chromium concentrations in leachates exceeded the European threshold ones. Amorpha fruticosa and Robina pseudoacacia grown in the artificial soils had different effects on cadmium, nickel, chromium, and copper leaching behavior. Amorpha fruticosa resulted in higher Ni and Cu concentrations in leachates, while Robina pseudoacacia enhanced leaching concentration of Cr.

In-situ cadmium phytoremediation using Solanum nigrum L.: the bio-accumulation characteristics trail.

In this study, Solanum nigrum L. was used in-situ for Cdphytoremediation in Cd polluted soil on Shenyang Zhangshi Irrigation area (SZIA) in 2008. The performance of the plant over the whole growth stage was assessed. Results showed, during the whole experimental stage, the aboveground biomass of single Solanum nigrum L. grew by a factor of 190, from 1.6 +/- 0.4 g to 300.3 +/- 30.2 g with 141.2 times extracted Cd increase from 0.025 +/- 0.001 to 3.53 +/- 0.16 mg. Both the distribution of biomass and amount of extracted Cd in the above-ground part of the plant changed according to the growth of the plant. Particularly, the percentage of biomass and extracted Cd in the stem increased from 20% to 80% and from 11% to 69%, respectively. The bioconcentration factor and transfer factor both varied significantly during the growth of the plant and the lowest values were measured at the flowering stage (0.94 +/- 0.31 and 3.48 +/- 1.14 respectively). The results in this paper provide reference values for the future research on the application of Solanum nigrum L. in phytoremediation and on chemical or/and agricultural strategies for phytoextraction efficiency enhancement.

[Ecotoxicity of synthetical musks on wheat (Triticum aestivum) based on seed germination].

With soil culture the ecotoxicological effects of galaxolide (HHCB) and tonalide (AHTN) on the germination of wheat (Triticum aestivum) seeds were investigated. And the influence of these two synthetical musks on the wheat germination rate, inhibition rate of root elongation and inhibition rate of shoot elongation were studied. The results showed that there were no obvious dose-effect relationship between wheat germination rate and concentrations of these two synthetical musks. Lower dose (HHCB < or = 150 mg x kg(-1), AHTN < or = 200 mg x kg(-1)) could accelerate the germination of wheat. Under the test concentrations of synthetical musks, the wheat germination rates treated with HHCB and AHTN were 77.78%-95.56% and 84.44%-97.78%, respectively. There were good dose-effect relationship between inhibition rate of root elongation (or inhibition rate of shoot elongation) and synthetical musks concentrations. The EC50 of HHCB and AHTN based on shoot were 155.84 mg x kg(-1) and 290.58 mg x kg(-1), and were 215.66 mg x kg(-1) and 323.10 mg x kg(-1) based on root from linear model. The EC50 of wheat sensitive positions showed that the toxicity of HHCB was stronger than AHTN.

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis.

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.

Changes in microbial populations and enzyme activities during nitrogen biodegradation of domestic sewage treatment in the Subsurface Wastewater Infiltration System (SWIS).

During the process of domestic sewage treatment in the Subsurface Wastewater Infiltration System (SWIS), changes in the microbial populations (nitrifying and denitrifying bacteria) and enzyme activities (urease, nitrate reductase and nitrite reductase) involved in the nitrogen removal process were evaluated over a 2-year period. The results showed nitrifying bacteria number declined with depths increasing, while denitrifying bacteria increased, both of which increased nearer the inlet. The depth for nitrate reductase activity from high to low in sequence was 0.3, 0.5, 0.7, 0.9 and 1.1 m. For nitrite reductase, the sequence was 0.5, 0.3, 0.7, 0.9 and 1.1 m. Urease and nitrite reductase activities were in positive correlation with the total nitrogen removal efficiency, with correlation coefficients 0.8662 and 0.9140, respectively and could be alternative to monitor the nitrogen biodegradation process in SWIS.

Study on nitrogen removal enhanced by shunt distributing wastewater in a constructed subsurface infiltration system under intermittent operation mode.

Subsurface wastewater infiltration system is an efficient and economic technology in treating small scattered sewage. The removal rates are generally satisfactory in terms of COD, BOD(5), TP and SS removal; while nitrogen removal is deficient in most of the present operating SWIS due to the different requirements for the presence of oxygen for nitrification and denitrification processes. To study the enhanced nitrogen removal technologies, two pilot subsurface wastewater infiltration systems were constructed in a village in Shenyang, China. The filled matrix was a mixture of 5% activated sludge, 65% brown soil and 30% coal slag in volume ratio for both systems. Intermittent operation mode was applied in to supply sufficient oxygen to accomplish the nitrification; meanwhile sewage was supplemented as the carbon source to the lower part in to denitrify. The constructed subsurface wastewater infiltration systems worked successfully under wetting-drying ratio of 1:1 with hydraulic loading of 0.081 m(3)/(m(2)d) for over 4 months. Carbon source was supplemented with shunt ratio of 1:1 and shunt position at the depth of 0.5m. The experimental results showed that intermittent operation mode and carbon source supplementation could significantly enhance the nitrogen removal efficiency with little influence on COD and TP removal. The average removal efficiencies for NH(3)-N and TN were 87.7 ± 1.4 and 70.1 ± 1.0%, increased by 12.5 ± 1.0 and 8.6 ± 0.7%, respectively.

Strategies for enhancing the phytoremediation of cadmium-contaminated agricultural soils by Solanum nigrum L.

Field trials contribute practical information towards the development of phytoremediation strategies that cannot be provided by laboratory tests. We conducted field experiments utilizing the Cd hyperaccumulator plant Solanum nigrum L., on farmland contaminated with 1.91 mg kg(-1) Cd in the soil. Our study showed that S. nigrum has a relatively high biomass. Planting density had a significant effect on the plant biomass and thus on overall Cd accumulation. For double harvesting, an optimal cutting position influenced the amount of Cd extracted from soils. Double cropping was found to significantly increase the amount of Cd extracted by S. nigrum. Fertilizing had no significant effect on plant biomass or on the Cd remediation of the soil over the short-term period. Our study indicates that S. nigrum can accumulate Cd from soils where the concentrations are relatively low, and thus has application for use in decontamination of slightly to moderately Cd-contaminated soil.

Impacts of crab bioturbation on the fate of polycyclic aromatic hydrocarbons in sediment from the Beitang estuary of Tianjin, China.

Bioturbation by the burrowing crab Helice tiensinensis was investigated to determine its impact on polycyclic aromatic hydrocarbon (PAH)-contaminated estuarine sediments. The concentrations of 16 U.S. Environmental Protection Agency (U.S. EPA) priority PAHs in sediment and pore water from a crab bed (including surface and burrow samples) and a control area, as well as in crabs, were measured. The total concentration of the 16 U.S. EPA priority PAHs in surface sediment of the crab bed (average 2,772 ng/g dry weight) was significantly higher than in the control area (1,173 ng/g dry weight). In the crab bed, the total concentration of PAHs in burrow sediment (1,239 ng/g dry weight) was lower than in surface sediment, and a similar trend was found for most of the individual PAHs, except for indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene. The enhanced PAH desorption in the burrow, which could be attributed to the increase in dissolved organic matter in pore water as well as the mechanical mixing by the crab, is expected to increase PAH flux to the sea. In addition to increased flushing to the sea, incorporation of PAHs in crab biomass and metabolism of PAHs by the crab, stimulated microbial degradation, was proposed as an ignorable factor that lowered the PAH concentration in burrow sediment, because crab bioturbation increases the abundance and activity of microorganisms through several means. Log K(OW) and log K(OC) correlated well for individual PAHs in sediment in the control area, although this correlation was poor for sediments in the crab bed. The log biota-sediment accumulation factor (BSAF) of PAHs exhibited a negative relationship with log K(OW), suggesting that the bioaccumulation of sorbed PAHs was controlled primarily by their bioavailability.

Poultry manured Bidens tripartite L. extracting Cd from soil - potential for phytoremediating Cd contaminated soil.

Pot experiment was conducted in a net house to evaluate the effects of poultry manure on a newly found Cd accumulator Bidens tripartite L. phytoextraction potential to soil Cd pollution. The average Cd concentrations in root, stem, leaf, inflorescence and shoots of poultry manured B. tripartite were significantly decreased (p<0.05) by 35.5%, 34.4%, 31.0%, 46.5% and 22.6%, respectively, as compared to that of without the addition of poultry manure due to the decrease of extractable Cd in soil. However, Cd extraction capacities (microgpot(-1)) in shoot of B. tripartite were significantly increased (p<0.05) due to more than 4-fold increase in shoot biomass. Thus, poultry manure application lowered extractable Cd in soil thereby significantly decreased its uptake, however increased plant biomass and enhanced the Cd phytoextracting efficiency.