Characteristics and source identification of fine particulate n-alkanes in Beijing, China

Ambient particulate n-alkanes were determined for fine particle (PM2:5) samples collected from Sep 2003 to July 2004 in Beijing, China. The average concentration of total n-alkanes (Pn-alkanes) from C11 to C34 was 425.72 ng/m3, ranged from 7.02 to 2893.28 ng/m3. The concentration distributions of n-alkanes homologues in this study exhibited peaks at C21 and C29 in heating season, and C29 in non-heating season. The average carbon preference index (CPI) value was 1.88 in the range of 1.18–3.88. The maximum CPI in summer indicated the contribution of biogenic origins such as plant wax; while the minimum CPI value in winter was probably a result of fossil fuel combustion. Preliminary estimation from these results showed that 59% of the n-alkanes in PM2:5 in Beijing summer originated from plant wax, while 74%–88% was from fossil fuel combustion in other three seasons. Source estimation was further performed using principal component analysis method. Two major components were yielded accounting for 57.3% and 30.9% of the total variance, which presented the fossil fuel and biogenic contribution, respectively.     

Sensitized effect of β-cyclodextrin on the fluorescence in the determination of carbaryl

Based on the significant enhancement of fluorescence intensity of carbaryl in inclusion complex, a spetrofluorimetdc method with high sensitivity was developed for the determination of carbaryl in aqueous solution. Under the optimum conditions, the complex had excitation and emission maxima at 278 nm and 332 nm, respectively. The linear range of the method was 7.0 ng/ml-1500 ng/ml with a detection limit of 1.2 ng/ml. The proposed method was successfully used to determine quantitativelv of carbarvl in cottonseeds.     

Monitoring gas- and particulate-phase short-chain polychlorinated paraffins in the urban air of Dalian by a self-developed passive sampler

The concentration of short-chain polychlorinated paraffins(SCCPs) in the urban air of Dalian,China was monitored from September 2016 to August 2017 with a self-developed passive sampler(PAS1) and an active high-volume sampler, simultaneously. PAS1 successfully collected the entire target SCCPs in the ambient air. Air SCCPs sampled by PAS1 were found be in the linear uptake stage during 181 days of sampling. Passive and active samples showed comparable congener profiles, and the dominant contributors of SCCPs in the two kinds of samples were similar. A significant linear correlation was observed between the total concentration of SCCPs sampled by PAS1 and active sampler in the four seasons. The passive sampling rates of the PAS1 for the gas and particulate phases of SCCPs were measured. The quantitative structure–property relationship of the sampling rate of PAS1(Rair) for gas-phase SCCPs was studied. From the molecular point of view, Rairwas mainly affected by the molecular weight and sub-cooled liquid vapor pressure of SCCPs. In general, SCCPs in the urban air of Dalian mainly existed in gas phase,lower molecular weight SCCPs primarily occurred in the gas phase, whereas higher molecular weight SCCPs were predominately adsorbed or absorbed on airborne particles. The air concentration of SCCPs in the four seasons were different, the correlation of the concentration of SCCPs in the air with the meteorology parameters was conducted. The exposure risk by intake air SCCPs of the residents around the sampling sites was evaluated according to the European risk assessment standards.     

Estimation of bioaccessibility and potential human health risk of mercury in Chinese patent medicines

Mercury(Hg), mainly in cinnabar species, has been used in medicine for thousands of years in China, and worldwide concern has been raised on its toxicity. In this work, the amount of bioaccessible mercury in 16 Chinese patent medicines(CPMs) was measured by using an in vitro simulated digestion system, consisting of simulated gastric and intestinal fluid, to investigate the bioavailability of mercury in CPMs and evaluate its potential risk to human health. Total mercury and mercury in the gastrointestinal extracts were measured by inductively coupled plasma mass spectrometry(ICP-MS). The levels of total Hg in 16 CPMs ranged from not detected to 11.89 mg/g, with a mean value of 1.13 mg/g, while the extractable Hg ranged from not detected to 4.37 μg/g, with a mean value of 0.42 μg/g.Mercury bioaccessibility varied significantly in the investigated CPMs, depending on the ingredient. Compared to the CPMs without cinnabar(2.5%–30.9%), the percentage of mercury in the gastrointestinal supernatants for CPMs with cinnabar was quite a bit lower(0.037%). By comparing with the Food and Agricultural Organization/World Health Organization Joint Expert Committee on Food Additives(FAO/WHO) safety guideline, the average daily intake dose(ADD) of Hg in the medicines was then calculated to access the risk of mercury to human health from taking CPMs.     

Quantitative determination of AI-2 quorum-sensing signal of bacteria using high performance liquid chromatography–tandem mass spectrometry

Autoinducer 2(AI-2), an important bioactive by-product of the Lux S-catalyzed S-ribosylhomocysteine cleavage reaction in the activated-methyl-cycle, has been suggested to serve as a universal intra- and inter-species signaling molecule. The development of reliable and sensitive methods for quantitative determination of AI-2 is highly desired.However, the chemical properties of AI-2 cause difficulty in its quantitative analysis.Herein, we report a high performance liquid chromatography-tandem mass spectrometric method that enables reproducible and sensitive measurement of AI-2 concentrations in complex matrixes. 4,5-Dimethylbenzene-1,2-diamine(DMBDM), an easy-to-obtain commercial reagent, was used for the derivatization treatment. The assay was linear in the concentration range of 1.0–1000 ng/m L(R~2= 0.999) and had a lower limit of quantification of0.58 ng/m L. The method exhibited several advantages, e.g., high selectivity, wide linear response range, and good sensitivity. Furthermore, the effectiveness of the method was further validated through measuring AI-2 concentrations in the cell-free culture supernatant from Escherichia coli wild type.     

Determination of total arsenic by photo-decomposition of organoarsenic compounds and hydride generation electrothermal atomic absorption spectrometry

A method was developed for the determination of total arsenic concentration in less than ng/ml level by decomposition of organoarsenicals using photo -oxidation combined with in situ trapping of arsenic hydride on a palladium coated graphite tube with subsequent atomization and detection by AAS. The organoarsenicals include monomethylarsenic, dimethylarsenic, arsenobetaine, arsenocholine, o -aminobenzenarsenate and p -aminobenzenarsenate. The method is simple and sensitive. Detection limit was obtained from different arsenic compounds over the range from 0. 058 to 0.063 ng/ml as As (based on three times of the standard deviation of 10 blank measurements) and the relative standard deviations for ten replicate measurements were from 2.0 to 3.8%. The calibration curves of arsenic compounds including inorganic and organic arsenicals were linear over the range from 0.1 to 3.0 ng/ml as As. The recommended method has been applied to the determination of total arsenic in tap and lake water samples at ng/ml leve     

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.     

Levels, distributions, and sources of legacy and novel per- and perfluoroalkyl substances (PFAS) in the topsoil of Tianjin, China

Soil is a major sink for per- and perfluoroalkyl substances (PFAS), wherein PFAS may be transferred through the food chain to predators at upper trophic levels, which poses a threat to human health. Herein, the concentrations and distributions of legacy and novel PFAS in topsoil samples from different functional areas in Tianjin were comprehensively investigated. Seventeen PFAS congeners were identified, with concentrations ranging from 0.21 ng/g to 5.35 ng/g, with a mean concentration of 1.25 ng/g. The main PFAS in the topsoil was perfluorooctanoic acid (PFOA). 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA; <MDL–1.95 ng/g, mean 0.11 ng/g), as an emerging substitute for perfluorooctane sulfonate (PFOS), was also detected in the topsoil. It showed slightly higher concentrations than PFOS (<MDL–1.62 ng/g, mean 0.10 ng/g), indicating it has gradually replaced legacy PFOS in this area. Based on the positive-definite matrix factor (PMF) receptor model, the major PFAS sources was dominated by textile treatment, metal electroplating plants, and some potential precursors of PFAS with longer chains (>C8) were the major sources (43.4%), followed by food packaging as well as coating materials (25.5%). In addition, Spearman correlation analysis and the structural equation model showed that population density significantly impacted the PFAS distribution in the topsoil of Tianjin.     

Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area

In order to understand the size distribution and the main kind of heavy metals in particulate matter on the lead and zinc smelting affected area, particulate matter(PM) and the source samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and the results were discussed and interpreted. Atmospheric particles were collected with different sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of different sizes, collected from the air and from factories, were measured using an inductively coupled plasma mass spectrometry(ICP-MS). The results indicated that the average concentration of PM, chromium(Cr), arsenic(As), cadmium(Cd) and lead(Pb) in PM was177.3 ± 33.2 μg/m~3, 37.3 ± 8.8 ng/m~3, 17.3 ± 8.1 ng/m~3, 4.8 ± 3.1 ng/m~3 and 141.6 ± 49.1 ng/m~3,respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM size distribution was at 1.1–2.1 μm, followed by 9–10 μm. The size distribution of As, Cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of1.1–2.1 μm and 9–10 μm ranges while for Cr, only a single-mode at 4.7–5.8 μm was observed. PM(64.7%), As(72.5%), Cd(72.2%) and Pb(75.8%) were associated with the fine mode below 2.1 μm,respectively, while Cr(46.6%) was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting sources.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.