Decolorization of Orange II using an anaerobic sequencing batch reactor with and without co-substrates

We investigated the decolorization of Orange II with and without the addition of co-substrates and nutrients under an anaerobic sequencing batch reactor (ASBR). The increase in COD concentrations from 900 to 1750 to 3730 mg/L in the system treating 100 mg/L of Orange II-containing wastewater enhanced color removal from 27% to 81% to 89%, respectively. In the absence of co-substrates and nutrients, more than 95% of decolorization was achieved by the acclimatized anaerobic microbes in the bioreactor treating 600 mg/L of Orange II. The decrease in mixed liquor suspended solids concentration by endogenous lysis of biomass preserved a high reducing environment in the ASBR, which was important for the reduction of the Orange II azo bond that caused decolorization. The maximum decolorization rate in the ASBR was approximately 0.17 g/hr in the absence of co-substrates and nutrients.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

气相色谱法测定柑橘和土壤中螺螨酯残留

以丙酮为提取剂,二氯甲烷为萃取剂,采用弗罗里硅土柱净化,气相色谱-电子捕获检测器测定柑橘和土壤中的螺螨酯残留,优化了样品前处理条件。方法在0.141μg/L～5.65 mg/L范围内线性良好,最低检出限为0.003 5 mg/kg,空白样品在0.050 mg/kg、0.500 mg/kg、1.00 mg/kg 3个添加水平上的平均回收率为82.2%～110%,平行测定的RSD为2.6%～9.8%。     

Enhanced Co-Metabolism of TCDD in the Presence of High Concentrations of Phenoxy Herbicides

Chemical residue studies were conducted from 1977-1987 on sites where spills of Agent Orange had occurred in the Herbicide Storage Sites at the Naval Construction Battalion Center, Gulfport, Mississippi, and on Johnston Island, Central Pacific Ocean. The soil persistence time of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was significantly decreased when in the presence of massive amounts of phenoxy herbicides (> 62,000 microg of herbicide/g of soil). Although microbial populations doubled in the most highly contaminated sites, fungal species diversity decreased. The dominant fungal species that appeared to be associated with the metabolism of the residues were of the genera Penicillium, Mucor, and Fusarium. TCDD level decreased from a mean high of 180 ng/g (ppb) to less than 1 ng/g of soil over a ten-year period.     

Environmental fate and bioavailability of agent orange and its associated dioxin during the vietnam war

BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.     

Engineered FeVO4/CeO2 nanocomposite as a two-way superior electro-Fenton catalyst for model and real wastewater treatment

FeVO₄/CeO₂ was applied in the electro-Fenton (EF) degradation of Methyl Orange (MO) as a model of wastewater pollution. The results of the characterization techniques indicate that FeVO₄ with triclinic structure and face-centered cubic fluorite CeO₂ maintained their structures during the nanocomposite synthesis. The effect of applied current intensity, initial pollutant concentration, initial pH, and catalyst weight was investigated. The MO removal reached 96.31% and chemical oxygen demand (COD) removal 70% for 60 min of the reaction. The presence of CeO₂ in the nanocomposite plays a key role in H₂O₂ electro-generation as a significant factor in the electro-Fenton (EF) system. The metal leaching from FeVO₄/CeO₂ was negligible (cerium 4.1%, iron 4.3%, and vanadium 1.7%), which indicates that the active species in the nanocomposite are strongly interacting with each other and are stable. The performance of the nanocatalyst in real wastewaters, salty, and binary systems was acceptable and the pollutions were removed efficiently. The synergistic effect between V, Fe, and Ce could be account as the reason for the respectable function of FeVO₄/CeO₂. The electron transfer proceeds via Haber-Weiss mechanism. A degradation pathway was proposed through by-products analysis using gas chromatography-mass spectrometry (GC–MS) technique. The pseudo-first-order kinetic model described the obtained experimental results (R² = 0.9906). The electro-Fenton system efficiency was improved by adding persulfate. The nanocomposite preserved almost its efficiency after six cycles. The obtained results demonstrate that the synergistic catalyst (FeVO₄/CeO₂) has the capability to introduce as a promising replacement of conventional catalysts in the electro-Fenton processes with brilliant proficiency.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

DIQUAT DISTRIBUTION IN WATER AFTER APPLICATION TO SUBMERSED WEEDS1

ABSTRACT: Diquat herbicide and rhodamine WT dye were applied in a lake to three 1.6 ha plots either with a polymer, which reportedly aids in sinking and confinement of aquatic herbicides, or without a polymer. Diquat and dye concentrations were measured at three different depths in the water column within the plots during the first three hours after application to determine vertical distribution of diquat and dye, and in composite samples at fixed distances from the plot up to 168 hours after application to determine movement out of the treated plots. Diquat and dye were homogeneous in the water column when no polymer was used, but were concentrated near the surface when polymer was used. This distribution may have resulted from temperature stratification. Polymer did not affect movement of diquat or dye out of the plots. The half-lives of diquat within the plots were 25 (SE=6.2) hr, 39 (SE=4.3) hr, and 25 (SE=2.0) hr. Forty-six percent of samples collected at the edges of the plots did not contain detectable diquat residues and only 66 percent of those samples with detectable diquat contained greater than the potable water tolerance (10 ppb). Diquat was not found in any samples 168 hours after application 61 m or farther from the edge of the plots. Dye and diquat concentrations were weakly correlated within and outside the plots. Dye half-lives were consistently higher than diquat, which suggests that the herbicide was removed from the water by plants and sediments more rapidly than dye.     

微波干燥制备Ag/TiO2的光催化活性试验研究

利用钛酸丁酯溶胶—凝胶法制备TiO2凝胶,通过光化学沉积法在TiO2凝胶表面负载Ag,采用微波对凝胶进行干燥制备TiO2光催化剂。以甲基橙为模拟污染物进行光催化降解试验,结果表明该方法制备的Ag/TiO2催化剂光催化活性明显提高。