Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

Open image in new window

     

Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s^–1). At the Beijing station, sulfur dioxide (SO₂) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO₂ emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO₂ emissions and incorporating heterogeneous oxidation of dissolved SO₂ by nitrogen dioxide (NO₂) on sulfate formation during winter haze. The results suggest that doubling SO₂ emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO₂ by NO₂ substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO₂ to sulfate conversion in the HetS (heterogeneous oxidation by NO₂) case reduces SO₂ concentrations, it is still largely overestimated by the model, indicating the overestimations of SO₂ concentrations in the North China Plain (NCP) are mostly due to errors in SO₂ emission inventory.

Open image in new window

     

Approaching the binding between Cu(II) and aerobic granules by a modified titration and µ-XRF

Interactions between metals and activated sludge can substantially affect the fate and transport of heavy metals in wastewater treatment plants. Therefore, it is important to develop a simple, fast and efficient method to elucidate the interaction. In this study, a modified titration method with a dynamic mode was developed to investigate the binding of Cu(II), a typical heavy metal, onto aerobic granules. The titration results indicated that pH and ionic strength both had a positive effect on the biosorption capacity of the granular sludge. The µ-XRF results demonstrated that the distribution of metals on the granular surface was heterogeneous, and Cu showed strong correlations and had the same “hot spots” positions with other metal ions (e.g., Ca, Mg, Fe etc.). Ion exchange and complexing were the main mechanisms for the biosorption of Cu(II) by aerobic granules. These results would be beneficial for better understanding of Cu(II) migration and its fate in wastewater treatment plants.     

Successful full‐scale enhanced anaerobic dechlorination at a NAPL strength 1,1,1‐TCA source area

Bioremediation of 1,1,1‐trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate‐reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full‐scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA‐ and pH‐related inhibition. © 2012 Wiley Periodicals, Inc.     

Characterization and Release Kinetics of Allylthiosufinate and its Transforments from Poly(d,l-Lactide) Microspheres

In this work was described poly(d,l-lactide) microwave synthesis using tin(II) 2-ethylhexanoate initiated ring-opening polymerization. Polymerization was performed at 100 °C with monomer to initiator molar ratio ([M]/[I]) of 5,000 in 30 min. The achieved number average molar mass of obtained polymers (determined by gel permeation chromatography) was 102,320 g/mol, with the polydispersion index, Q, 2.80. Structural characterization was performed by FT-IR spectroscopy followed characteristic bands. For applicative purposes the obtained polymer was purified during the procedure of microsphere preparation. Biodegradable microspheres prepared from poly(d,l-lactide) have been widely studied in recent years and have become well established controlled drug delivery systems. In this work microspheres were loaded with allyl thiosulfinate (allicin) and its transforments products (ajoene and vinyldithiine), as pharmacological active substances. The morphology of the microspheres was analyzed using a scanning electron microscope. Allicin was synthesized by acid oxidation of allyl disufide and purification of obtained products by liquid–liquid extraction with diethyl ether. Obtained allicin, purity 73%, was transformed using microwave in acetone solution, at solvent boiling temperature, for 5 min. For the quality and quantity analysis of allicin and its transformation process was used LC/MS chromatography. (E)- and (Z)-ajoene were detected at retention time 3.1 and 3.3 min, respectively, whence 3-vynil-4H-1,2-dithiine and 2-vynil-4H-1,3-dithiine were detected at 4.3 and 4.8 min, respectively. Retention time of allicin was 2.93 min, according to liquid chromatography results. HPLC method was used for assessment of pharmaceutical substances (alicine and alicine transforments) releasing from microspheres at room temperature in solutions with different pH (pH = 3 and pH = 8) for 24 h.     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

PET from Used Beverage Bottles: A Material for Preparation of Biologically Degradable Copolyesters

Poly(ethylene terephthalate) from used colorless beverage bottles was solvolyzed by ethane-1,2-diol. Hydroxyl end-groups present in the mixture of polyols formed were used to initiate the polymerization of ??-caprolactone (CLO) at 190?°C. Polycondensation (190?°C) of the reaction mixture containing an equilibrium amount of lactone corresponding to the reaction temperature yield an aliphatic?Caromatic copolyester. A variety of copolyesters containing 20?C60?mol. % CLO structural units was prepared. The microstructure of their macromolecules was analyzed using ¹H?NMR spectroscopy. Copolyesters were characterized by thermal analysis and tensile tests and their biodegradation potential was checked by the composting test.     

Synthesis of Polylactide-b-Poly (Dimethyl Siloxane) Block Copolymers and Their Blends with Pure Polylactide

The synthesis of polylactide (PLA)-b-poly (dimethyl siloxane) (PDMS) linear block copolymers and their use in blends with pure-PLA are described. PLA-b-PDMS linear block copolymers were obtained by the transesterification reaction in chloroform solution between poly(dimethyl siloxane) bis (2-aminopropyl ether) (molecular weight 2,000?Da) with PLA in the presence of stannous octoate. Molecular weights (Mw) of the block copolymers were varied from 53,800 to 63,600?Da while that of pristine PLA was 73,600?Da. The copolymers obtained were purified by fractional precipitation and then characterized by ¹H NMR, FTIR, GPC, viscometry and DSC techniques. Blends of pure PLA with PLA-b-PDMS block copolymers displayed improved elastic properties (elongation up to 140%) compared to pure PLA (elongation ~9%). Thermal, mechanical and morphological characterization of the blends were also conducted.     

Substance flow analysis for an urban drainage system of a representative hypothetical city in China

This paper discusses the use of substance flow analysis (SFA) as a tool to support quantified research on urban drainage systems. Based on the principle of mass balance, a static substance flow model is established to describe and examine the routes and intensities of water, chemical oxygen demand (COD), total nitrogen (TN) and total phosphorus (TP) for a representative hypothetical city (RH city) in China, which is a devised and scaled city using statistical characteristics of urban circumstances at the national level. It is estimated that the annual flux of water, COD, TN and TP through the urban drainage system in 2010 was 55.1 million m³, 16037.3 t, 1649.5 t and 209.7 t, respectively. The effluent of wastewater treatment plant (WWTP) was identified as the most important pathway for pollutant emissions, which contributed approximately 60% of COD, 65% of TN and 50% of TP to receiving water. During the wastewater treatment process, 1.0 million m3, 7042.5 t, 584.2 t and 161.4 t of the four studied substances had been transmitted into sludge, meanwhile 3813.0 t of COD and 394.0 t of TN were converted and emitted to the atmosphere. Compared with the representative hypothetical city of 2000, urban population and the area of urban built districts had expanded by approximately 90% and 80% respectively during the decade, resulting in a more than threefold increase in the input of substances into the urban drainage system. Thanks to the development of urban drainage systems, the total loads of the city were maintained at a similar level.     

Arsenic bioaccessibility in a gold mining area: a health risk assessment for children

High concentrations of total arsenic (As) have been measured in soils of gold mining areas of Brazil. However, bioaccessibility tests have not yet been conducted on those materials, which is essential for better health risk estimates. This study aimed at?evaluating As bioaccessibility in samples from a gold mining area located in Brazil and assessing children's exposure to As-contaminated materials. Samples were collected from different materials (a control and four As-contaminated soils/sediments) found in a gold mine area located in Paracatu (MG), Brazil. Total and bioaccessible As concentrations were determined for all samples. The control soil presented the lowest As concentrations, while all other materials contained high total As concentrations (up to 2,666?mg?kg(-1)) and low bioaccessible As percentage (<4.2%), indicating a low risk from exposure of resident children next to this area. The calculated dose of exposure indicated that, except for the pond tailings, in all other areas, the exposure route considering soil ingestion contributed at most to 9.7% of the maximum As allowed ingestion per day (0.3?μg?kg(-1) BW day(-1)).