Atrazine contamination in agricultural soils from the Yangtze River Delta of China and associated health risks

Atrazine is one of the most widely applied and persistent herbicides in the world. In view of limited information on the regional contamination of atrazine in soils in China, this study investigated the spatial distribution and environmental impacts of atrazine in agricultural soils collected from the Yangtze River Delta (YRD) as an illustrative analysis of rapidly developing regions in the country. The results showed that the concentrations of atrazine in the YRD agricultural soils ranged from <1.0 to 113 ng/g dry weight, with a mean of 5.7 ng/g, and a detection rate of 57.7 % in soils. Pesticide factory might be a major source for the elevated levels of atrazine in Zhejiang Province. The contamination of atrazine was closely associated with land use types. The concentrations and detection rates of atrazine were higher in corn fields and mulberry fields than in rice paddy fields. There was no significant difference in compositions of soil microbial phospholipids fatty acids among the areas with different atrazine levels. Positive relationship (R = 0.417, p < 0.05, n = 30) was observed between atrazine and total microbial biomass. However, other factors, such as soil type and land management practice, might have stronger influences on soil microbial communities. Human health risks via exposure to atrazine in soils were estimated according to the methods recommended by the US EPA. Atrazine by itself in all the soil samples imposed very low carcinogenic risks (<10^?6) and minimal non-cancer risks (hazard index <1) to adults and children.     

春季香溪河库湾CODMn时空分布及其影响因子初探

于2012年春季在香溪河库湾合理布置断面观测,分析水体高锰酸盐指数(CODMn)的时空分布特征,并对CODMn与水体中叶绿素a、溶解氧(DO)、水体垂向稳定系数、总氮(TN)和溶解性硅酸盐(D Si)进行相关分析,以期为香溪河流域有机污染的治理提供支持和指导。结果表明：春季香溪河库湾CODMn浓度变化范围为1.40～5.36 mg/L,4月CODMn均值明显高于3月和5月,为366 mg/L,整个春季CODMn浓度从下游至上游呈现明显增大的趋势。相关分析发现,春季水华暴发期间,CODMn与叶绿素a显著正相关(分别为072和074),而在未暴发水华的3月二者的相关性不显著。浮游植物和水体稳定系数是影响CODMn变化的主要因素。倒灌异重流使得高含氮、低CODMn浓度的长江干流水体进入库湾下游并稀释CODMn浓度。CODMn与DO在3月和5月的弱相关关系为香溪河CODMn特殊的分布特征提供了其它合理的解释,其分布特征受多种因素的共同影响。春季库湾上游有机污染趋于恶化,限制支流特别是上游污染物的排放是改善有机污染现状的有效途径     

Comparative Thermodynamic Study on the Contribution of the Autocondensation and Copolymerization Reactions for the Tannins of the Subspecies of Acacia nilotica

Autocondensation and copolymerization reactions of the Acacia nilotica subspecies tomentosa (Ant) and the subspecies adansonii (Ana) tannins extracts solutions have been studied at several pH values by thermomechanical analyzer. Results of chemical analysis of these tannins revealed that the studied tannins, Ant and Ana contained high percentages of extractable tannins (54 and 57 %) for and polyphenolic materials (78 and 80 %) respectively. Different hardeners such as paraformaldehyde, Urea and pMDI were added at different ratios and their polycondensation reactions was studied and compared with their autocondensation ones. The aim was to evaluate the tannins suitability for the production of commercially and technically viable tannin adhesives with reduced Formaldehyde emission for wood products and to study the interference between the autocondensation and the copolymerization reaction. The obtained results of autocondensation reaction for both of the tannins studied showed that the best Young’s modulus values for Ant (3,500 and 2,750 MPa) and Ana (2,650 and 2,620 MPa) were obtained at pH 5 and 7. The Young’s modulus values obtained by the tannins Ant were higher than those achieved by Ana. This indicates that the Ant is more reactive than Ana. These results were also in line with results achieved by the gel time for both of the tannins. Gel time results indicate that the reactivity of both tannins increased towards alkalinity with Ana being more reactive at alkaline pH. Addition of 8 % of paraformaldehyde was adversely affecting the autocondensation reactions, as the best Young’s modulus values were achieved at pH 4 for Ant tannins. As for Ana the higher Young’s modulus values (2,000 and 2,310 MPa) were achieved at pH 5 and 7. This indicates that autocondensation reaction was contributed to the final network of the copolymerization reaction. When smaller ratio of paraformaldehyde and Urea (5 %) was added to Ant tannins it favors the autocondensation reaction and the best Young’s modulus values were obtained at pH 5 and 7. Addition of pMDI (10–30 %) was found to decrease the temperature of copolymerization and the obtained Young’s modulus values by Ant were lower than those obtained by autocodensation reaction. Best Young’ modulus values were obtained by Ant at pH 5 and 7. Ana gave the best Young’s modulus values at pH 4 and 5 indicating that the autocondensation appears to depress the copolymerization reactions. The obtained results by both reactions were very important from technical and economical point of view as they concluded that it is very possible to produce adhesives system with zero emission depending on the tannins autocondensation reaction and pH values. Reduction of formaldehyde emission was also possible upon addition of smaller amount of paraformaldehyde and Urea.     

Biodegradability of Epoxidized Soybean Oil Based Thermosets in Compost Soil Environment

In this study, bio-thermoset from epoxidized soybean oil (ESO) was prepared in the presence of methylhexahydrophthalic anhydride curing agent and 2-ethyl-4-methylimidazole catalyst. The crosslink densities of the synthesized ESO are ranged from 0.109 × 10^?3 to 0.308 × 10^?3 mol/cm³. The ESO bio-thermosets were exposed to the soil-burial test for 8 months. Weight change and morphology of the degraded ESO specimens were assessed. It was found that the weight loss of ESO was governed by the materials compositions, crosslink density and the soil-burial exposure time. The 3 mm thickness ESO bio-thermosets with crosslink density of 0.109 × 10^?3 mol/cm³ had fully biodegraded after soil-burial for 6 months. In addition, 16S rDNA sequencing was carried out to identify the soil microorganisms. It was suggested that Comamonas sp., Bacillus sp., Streptomyces sp. and Acinetobacter sp. are the possible soil microbes that degrade the ESO bio-thermosets in the compost soil environment.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

Gas-phase and semivolatile organic emissions from a modern nonroad diesel engine equipped with advanced aftertreatment

ABSTRACT

U.S. Tier 4 Final and Euro Stage IV and V regulations for nonroad compression-ignition engines have led to the development of exhaust aftertreatment technologies optimized for nonroad engines and duty cycles. In this study, several aftertreatment configurations consisting of state-of-the-art diesel oxidation catalysts (DOCs), diesel particulate filters (DPFs), copper (Cu) zeolite– and vanadium-based selective catalytic reduction (SCR) catalysts, and ammonia oxidation (AMOX) catalysts are evaluated using both nonroad transient (NRTC) and steady (8-mode NRSC) cycles in order to understand both component- and system-level effects of diesel aftertreatment on gas-phase, semivolatile, and particle-phase and particle-bound unregulated organic emissions. Organic emissions reported in this work include total hydrocarbon (THC), n-alkanes, branched alkanes, saturated cycloalkanes, aromatics, aldehydes, ketones, hopanes, steranes, and soluble organic fraction (SOF). Brake-specific emissions are reported for four configurations, including engine-out, DOC+CuZ-SCR+AMOX, V-SCR+AMOX, and DOC+DPF+CuZ-SCR+AMOX, and conversion of engine-out emissions is reported for the three aftertreatment configurations. Mechanisms responsible for the reduction of organic species are discussed in detail. This summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere with tools such as the U.S. Environmental Protection Agency’s Motor Vehicle Emissions Simulator (MOVES2014a) model.

Implications: Anthropogenic emissions are a source of significant human health and environmental risk. This study, focused on the treatment of exhaust emissions from a modern nonroad diesel engine with a variety of aftertreatment configurations, examines the impact that human industrial activity can have on air pollution. In particular, we focus on the remediation of gas-phase and semivolatile organic emissions by emission reduction technologies. This detailed summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere with tools such as the U.S. Environmental Protection Agency’s MOVES2014a model.     

Preparation and Characterization of Hydrogel Based on Poly(vinyl alcohol) Cross-Linked by Different Cross-Linkers Used to Dry Organic Solvents

Poly(vinyl alcohol) (PVA) hydrogels were chemically cross-linked with/without different cross-linkers such as glutaraldehyde and epichlorohydrin, in the presence of a catalyst, or activator (potassium hydroxide) to produce three types of hydrogels. The structures of PVA and the prepared gel types were determined by FTIR spectroscopy, the mechanical and thermal properties, of these hydrogels were examined. The effects of different pH values and temperatures on the swelling properties of the prepared gels were examined. From the obtained results, it was found that, the low concentration of the cross-linker produced hydrogel with moderate properties, but in absence of the cross-linker, the obtained hydrogel exhibited good properties and can be used as friendly environmentally moisture absorbents from the organic solvents. The insolubility and swelling properties of gels were tested in these solvents. The results indicated that these hydrogels can be used as moisture absorbents and solvent dryers.     

Comprehensive assessment of toxic metals in urban and suburban street deposited sediments (SDSs) in the biggest metropolitan area of China

A set of toxic metals, i.e. As, Hg, Pb, Cd, Cu, Zn, Ni and Cr, in urban and suburban SDSs were investigated comparatively in the biggest metropolitan area of China, Shanghai. Results showed that all of the metals except As were accumulated greatly, much higher than background values. Geo-accumulation index indicated that metal contamination in urban SDSs was generally heavier than that in suburban SDSs. Potential ecological risk index demonstrated that overall risks caused by metals were considerable. Cd contributed 52% to the overall risk. Multivariate statistical analysis revealed that in urban SDSs, Zn, Ni, Cd, Pb, Cu and Cr were related to traffic and industry; coal combustion led to elevated levels of Hg; soil parent materials controlled As contents. In suburban SDSs, Pb, Cu, As and Cd largely originated from traffic pollution; Zn, Ni and Cr were associated with industrial contaminants; Hg was mainly from domestic solid waste.     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.     

Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.