β-环糊精强化微生物修复石油烃污染土壤的试验研究

石油烃污染物的生物可利用性是土壤微生物修复的限制因素,为了提高污染物的生物可利用性和降解效率,引入环境友好的β-环糊精作为污染物增溶剂,并与表面活性剂十二烷基硫酸钠(SDS)作对比。结果表明,当β-环糊精的投加浓度为其在水中饱和溶解度的90%、SDS的投加浓度为其临界胶束浓度时,β-环糊精和SDS对土壤中石油烃污染物的增溶效果达到最大,分别为84.42%和89.63%。虽然两者都具有相近的增溶效果,但SDS具有一定的生物毒性,抑制了微生物的生长及其对石油烃污染物的降解,而β-环糊精可以促进微生物生长并有效提高微生物对污染物的去除效率。投加β-环糊精的微生物修复组在15 d内的降解率达到19.5%,比单独微生物修复组的降解率提高了70%以上。     

The effects of soil and Trifolium repens (white clover) on the fate of estrogen

In this study, we investigated the behavior of estrogens in the rhizosphere of white clover (Trifolium repens, clover hereafter) with two different pot tests, using soil and agar as growth media. In a pot test using agar spiked with estrogen, the estrogen concentration in the agar with clover decreased to non-detectable levels within one month, while in the agar without clover, 60% of initially added estrogen remained after one month. The half-lives of estrone (E1) and 17β -estradiol (E2) in the agar with clover were 2.4–3.8 and 13.2 d, respectively. The dissipation of E1 followed first-order rate law, while that of E2 fitted a zero-order reaction, indicating that they had different mechanisms of dissipation from agar. In the soil pot test, the behavior of E1 and E2 was not influenced by clover. An initial rapid decrease in the amount of estrogen extracted by methanol/acetic acid was followed by persistence for 1–3 months, regardless of presence of clover. Moreover, in three weeks E1 and E2 were only partly degraded by microbes extracted from the soil used in the pot test. In this study, abiotic degradation of estrogens and sorption of estrogen to soil, rather than the effects of soil microbes and clover, contributed to the initial rapid dissipation of estrogens in the soil. However, the results of the agar pot test suggested that vegetation such as clover may significantly contribute to removal of estrogens when estrogens in aqueous phase are discharged with surface runoff and preferential flow after heavy rain in agricultural fields, or when present in soils with low estrogen sorptivity.     

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Effects of hydroxypropyl-β-cyclodextrin on pyrene and benzo[α]pyrene: bioavailability and degradation in sotil

Effect of hydroxypropyl-β-cyclodextrin (HPCD) on the bioavailability and biodegradation of the polycyclic aromatic hydrocarbons (PAHs) pyrene (PYR) and benzo[α]pyrene (BaP) in spiked soils was investigated in 14-week incubation experiments. To evaluate the effect of HPCD in soils with a different matrix, humic substance (HS) was added into soil samples. A 6-h Tenax TA extraction method was used to evaluate pollutants bioavailability. The biodegraded and extracted fractions were compared to evaluate the impact of HPCD on PAHs biodegradation. Results indicated positive effects of HPCD on fast desorption behaviours of PAHs. The biodegraded fraction was consistent with that of the extracted for PYR. However, in terms of BaP, the results were contrary which suggests that biological factors may be limiting factors for BaP pollution remediation. HS weakened the HPCD solubilisation effect while accelerated the decay of PYR and BaP, also implying that bioavailability was not the sole factor limiting PAH biodegradation. In addition, analysis of microbial communities demonstrated that HPCD inhibited the growth of some soil bacteria while HS promoted the evolution of some soil microorganisms. A limited population of hydrocarbon degrader populations led to observing incomplete PAH biodegradation even in the presence of HPCD.     

用于磷吸附的载铁（β-FeOOH）沸石制备及特性

以天然沸石为载体,采用FeCl3水解法制备用于磷吸附的载铁沸石（β-FeOOH-Z）,优化β-FeOOH-Z的制备条件,包括FeCl,溶液浓度、负载pH值、负载时间、负载温度和烘干温度,并利用x射线衍射（XRD）和傅里叶变换红外光谱（FTIR）对β-FeOOH-Z及其磷吸附特性进行分析。结果表明,β-FeOOH-Z的优化制备条件为：FeCl3溶液浓度1mol／L、负载pH值6、负载时间24h、负载温度25℃和烘干温度60℃。优化制备条件下,100-120目沸石的载铁量为100．2mg／g,铁的负载率为18％,其磷吸附量为7．68mg／g,比天然沸石提高79．6％。XRD分析结果表明,β-FeOOH-Z中的杂质元素较天然沸石减少,并有效负载β-FeOOH;制备条件对β-FeOOH-Z的成分有较大影响,FeCl,溶液浓度较低、负载温度和烘干温度过高均使β-FeOOH-Z中含有α-Fe2O3,并导致其磷吸附效率降低。FTIR分析结果表明,β-FeOOH-Z的表面羟基在其吸附磷过程中起重要作用,羟基与磷酸根离子的配位交换是β-FeOOH-Z吸附磷的主要作用机制。     

Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Bio-efficacy evaluation of nanoformulations of β-cyfluthrin against Callosobruchus maculatus (Coleoptera: Bruchidae)

In the present investigation, bioefficacy of developed β-cyfluthrin formulations, utilizing laboratory synthesized poly(ethylene glycols) based amphiphilic copolymers, were evaluated against Callosobruchus maculatus (Coleoptera: Bruchidae). The bioefficacy data indicated that the formulations developed by utilizing polymers having PEG – 1500 (3c) and PEG – 2000 (3d) as the hydrophilic segment showed greater efficacy after 14 days as evident from EC₅₀ values (2.2 and 1.58 mg L^?1 respectively). Also, release from the commercial SC formulation was faster than developed formulations as the commercial formulation had the lowest EC₅₀ value on the first day (0.51 mg L^?1). The mean EC₅₀ of the commercial formulation against C. maculatus was quite high as compared to those of developed formulations. The results suggest that depending upon the polymer matrix used, the application rate of β-cyfluthrin can be optimized to achieve insect control at the desired level and period. The results described in this paper are promising and provide a comparison of developed formulations with the commercial one showing an earlier degradation of β-cyfluthrin in the latter and relatively prolonged activity in the former.     

Hp-β-环糊精包络臭氧氧化去除水中PPCPs研究

为提高臭氧的稳定性,采用臭氧化Hp-β-环糊精溶液的方法对臭氧进行包络。考察了臭氧/Hp-β-环糊精包络物的氧化特性,臭氧化量和Hp-β-环糊精浓度对臭氧/Hp-β-环糊精包络物氧化能力的影响,并研究了臭氧/Hp-β-环糊精包络物对二级出水中添加的10种药品和个人护理用品(PPCPs)的去除效果。结果表明:臭氧/Hp-β-环糊精包络物具有持续的氧化能力,增加臭氧化量或Hp-β-环糊精浓度可显著提升臭氧/Hp-β-环糊精包络物的氧化能力。臭氧/Hp-β-环糊精包络物有较强的氧化性;向0.7 g/L的Hp-β-环糊精溶液中通入6 mg臭氧后,PPCPs的去除率为50%~70%,去除率受PPCPs分子结构影响。臭氧/Hp-β-环糊精包络物氧化可与其他氧化技术联合应用于污染物去除或用作臭氧化后的持续氧化。     

Poly[β-(1→4)-2-amino-2-deoxy-D-glucopyranose] based zero valent nickel nanocomposite for efficient reduction of nitrate in water

Chemical reduction of nitrate using metal nanoparticles has received increasing interest due to over-dependence on groundwater and consequence health hazard of the nitrate ion. One major drawback of this technique is the agglomeration of nanoparticles leading to the formation of large flocs. A low cost biopolymeric material, poly [β-(1 → 4)-2-amino-2-deoxy-D-glucopyranose] (β-PADG) obtained from deacetylated chitin was used as stabilizer to synthesize zero valent nickel (ZVNi) nanoparticles. The β-PADG-ZVNi nanocomposite was characterized using infra red (IR), UV-Vis spectrophotometric techniques and Scanning Electron Microscope (SEM). The morphology of the composite showed that β-PADG stabilized-ZVNi nanoparticles were present as discrete particles. The mean particle size was estimated to be (7.76 ± 2.98) nm and surface area of 87.10 m²/g. The stabilized-ZVNi nanoparticles exhibited markedly greater reactivity for reduction of nitrate in water with 100% conversion within 2 hr contact owing to less agglomeration. Varying the β-PADG-to-ZVNi ratio and the ZVNi-to-nitrate molar ratio generally led to a faster nitrate reduction. About 3.4-fold difference in the specific reaction rate constant suggests that the application of the β-PADG-stabilizer not only increased the specific surface area of the resultant nanoparticles, but also greatly enhanced the surface reactivity of the nanoparticles per unit area.