Dechlorination of pentachlorophenol in supercritical carbon dioxide with zero-valent palladium-magnesium bimetallic mixture

A stream of substrate pentachlorophenol [PCP, 5 mg min(-1) in water-methanol (1 + 4, v/v)] was merged with 1.5 ml min(-1) of supercritical carbon dioxide (scCO2) and delivered to a reactor column (25 cm x 1 cm) of zero-valent palladium-magnesium mixture. The resulting dechlorinations, although very efficient, were not quantitative. For continuous operation at 400 degrees C for 6 h, phenol was the principal product, with lesser quantities of methylated products and only traces of chlorinated products (principally monochlorinated species). PCP deoxygenation was not observed and ring methylation was decreased relative to analogous reactions in hydroxylic organic solvent. With time, the reactor column slowly lost dechlorination activity. Reducing the loading of Pd0 on Mg0 from 2% to 1% (w/w) apparently did not change the course of the reaction; however, the dechlorination capacity was decreased correspondingly. None the less, over 6 h or 5 h of continued operation, the dechlorination efficiency was 0.995 for the 2% (w/w) loading of Pd0 on Mg0 and 0.984 for the 1% (w/w) loading.     

Estimates of total polychlorinated biphenyl (PCB) compounds in soils/sediments by hydrogenolysis to dicyclohexyl

A method to determine the total PCB content by hydrogenolysis (hydrodechlorination and hydrogenation) of chlorinated biphenyl compounds was extended to natural particulate matrices (soil and sediment). The contaminated soil was suspended in hexane in the presence of Pd/gamma-Al2O3 in a hydrogen atmosphere then permitted to react for one hour at 65 degrees C. Dicyclohexyl, recovered in the hexane, was quantified by gas chromatography mass spectrometry. The reaction was very efficient for soil/sediment in hexane suspension and virtually complete provided that excess catalyst was added to samples that were burdened with higher PCB loadings prior to reaction otherwise some partial hydrogenation of biphenyl was also observed. The proposed method was validated with the analysis of five certified reference materials.     

生活垃圾填埋场覆盖膜破损及其环境影响

中国的垃圾填埋场目前多采用高密度聚乙烯膜(HDPE)进行覆盖,已建成的填埋场均存在不同程度覆盖膜破损现象。采用填埋气泄漏可视化检测技术对中国东部某大型生活垃圾填埋场开展覆盖膜完整性检测,揭示了覆盖膜破损特征及破损成因,明确了破损点泄漏量,评估了其温室效应影响,梳理了国内外填埋场覆盖层监管相关管理规定和措施。结果表明:尖锐物体应力损伤导致的破损是填埋场覆盖膜破损的主要类型,粗放施工、监管机制不足、维护管理不到位是造成填埋场覆盖膜破损的主要原因。破损点的甲烷泄漏量约为817.2 m³/d,约合每年向大气环境释放温室气体超过4 900 t CO₂-eq。完善填埋场污染控制标准和技术规范、加强填埋场覆盖膜完整性的监管,是控制填埋场温室气体排放和推进固废处置设施碳减排的重要举措。     

Influence of formulation on mobility of metazachlor in soil

The mobility of metazachlor [2-chloro-N-(pyrazol-1-ylmethyl)acet-2′,6′-xylidide] in sand soil and loamy sand soil was studied in a soil column under laboratory conditions. Commercial metazachlor formulation (Metazachlor 500 suspension concentrate (SC)) and metazachlor immobilized in alginate matrix were used for leaching experiment. The initial concentration of metazachlor in soil for both formulations was 2.0 mg mL^?1. After application of herbicide, the columns were irrigated with 100, 40, and 3.7 mm of water. After 1 h, when addition of water was completed, soils were sampled in 5-cm segments and were used for the analysis of residues. The use of alginate controlled release (CR) formulation reduced the vertical mobility of metazachlor into soil layer in comparison with the formulation SC.     

Speciation of iron in river water using a specific catalytic determination and size fractionation

A comprehensive speciation scheme was proposed for the speciation of iron in river water (0.45 microm filtrate). The speciation was based on the catalytic determination of reactive iron as Fe3+ and Fe(III)Li/(3 -in)+, where i = 1 or 2 for a unidentate and i = 1 for a bidentate ligand, Ln-. The scheme incudes size fractionation and acid decomposition of the sample and determination of the coexisting species. The proposed scheme was applied to natural and artificial samples and acidified preparations of these. Resulting fractionation patterns of reactive and unreactive iron and of coexisting humic acid were useful for the characterization of iron species in the natural samples. The reactive iron in the molecular weight (Mr) > or = 10(4) fraction was associated with humic iron aggregates and estimated as iron complexed with them. The unreactive iron in this fraction dissociated in 0.1 M HCI and was estimated as iron in the aggregates of iron(III) hydroxide (s) and humic iron. From the fractionation results of the artificial sample, the reactive and unreactive iron in the Mr < 10(3) fraction may be formed by complexing simple anions like F- and C2O4(2-) at their naturally-occurring concentration levels. The fractionation results also suggested that humic acid and Si contributed to the formation of reactive and unreactive iron in the Mr > or = 10(4) fraction.     

Debromination of 1,4-Dibromobenzene and 4,4′-Dibromobiphenyl: A Model for Cleansing of PCBs

The aim of this study is to develop a catalytic method which has advantages over current method to detoxify and degrade environmentally harmful polychlorinated biphenyls (PCBs). A variety of catalysts have been employed in a preliminary study on 1,4-dibromobenzene and 4,4-dibromobiphenyl which may be considered to represent simple analogues of PCBs. The most satisfactory catalysts are those involving [Pd(dppf)] [dppf = 1,1-bis(diphenylphosphino)ferrocene], generated in situ from PdCl2(dppf) or Pd(dppf)2. In the presence of the reducing reagent, namely NaBH4, debromination has been achieved at relative mild conditions with high product yields (> 70%). Thus, our results indicate the possibility of dechlorination of PCBs with such catalysts.     

二氧化钛光催化技术处理制药废水的实验研究

通过改变二氧化钛浓度、调节pH值、添加H2 O2及铁离子浓度等实验方法,验证了二氧化钛光催化反应处理制药废水的效果。根据测定制药废水中氨氮、COD浓度,计算氨氮、COD的去除率,得出二氧化钛光催化反应的最佳反应条件,为实际应用提供依据。     

Recycling of complexometric extractants to remediate a soil contaminated with heavy metals

Equilibrations were performed with complexing reagent(s) to mobilise Cd, Cu, Mn, Ni, Pb and Zn from a contaminated urban soil. The metal-laden aqueous extract was treated with zero-valent magnesium (Mg0) or bimetallic mixture (Pd0/Mg0 or Ag0/Mg0) to precipitate the heavy metals from solution while liberating the chelating reagent(s). Post precipitation, the pH of aqueous supernatant fraction was readjusted to approximately 5 and the solution was re-combined with the soil particulates to extract more heavy metal pollutants. A sparing quantity of EDTA (10 mmoles) mobilised 32-54% of the 5 mmoles of heavy-metals from the soil with three cycles but only 0.1% of the iron was removed. Three successive extractions with a mixture of complexing reagents (3 mmoles), 1:1 EDTA plus HEDC [bis-(2-hydroxyethyl)-dithiocarbamate], mobilised approximately 49% of the Pb, approximately 18% of the Zn and approximately 19% of the Mn burden but only 7% of the Cu, and 1% of the Fe from this soil. An appreciable fraction of the mobilised Pb and Cu and a portion of the Zn was cemented to the surfaces of the excess magnesium whereas virtually all of the Fe and Mn was removed from solution as insoluble hydroxides.     

Assessment of workers' exposure to palladium in a catalyst production plant

Airborne particulate matter was collected and biomonitoring of workers was performed by sampling blood, urine and hair of 84 exposed subjects, 17 occasionally exposed employees, 21 controls from administrative offices and 25 unexposed people (external controls). Determination of Pd was performed using Quadrupole and High Resolution Inductively Coupled Plasma Mass Spectrometry. The Production of Catalysts Department and the Refining Service presented the highest levels of Pd in airborne matter collected by means of an area sampler. The highest level of soluble Pd (1.66 microg m(-3)) was found in the Production of Catalysts Department. The highest concentration of Pd in airborne matter, collected by means of personal devices (7.90 microg m(-3)) was found in the Refining Service. Hair showed a clear distribution pattern among departments, with values ranging from 0.60 to 5.54 microg g(-1). Administrative workers presented blood levels of Pd between 2 and 500 times higher than external controls. Only urine levels correlated with the measurements of airborne Pd collected with personal devices. A very strong association between airborne Pd collected by personal devices and Pd levels in hair (r(2)= 0.569, with p< or = 0.01) and urine (r(2)= 0.684, with p< or = 0.01) was found. On the basis of these findings: (i) blood results appear to be an unsuitable biological marker for occupational exposure to Pd; (ii) urine could be considered as a satisfactorily responsive bio-marker for occupational monitoring; and (iii) hair cannot be considered a good index of time-related exposure.     

Evolution of water chemistry in natural acidic environments in Yangmingshan,Taiwan

In Yangmingshan National Park, located in the northern part of the Taiwan Island, there is a very rare area where fish (Channa asiatica) live in spite of acid environments. The origin of the acid in local acid ponds and rivers and the evolution of the water chemistry are discussed on the basis of sulfur stable isotope ratios and chemical equilibria. One of the sources of the acid is sulfuric acid, which is derived from the oxidation of hydrogen sulfide in volcanic gas gushing out from fumaroles around the area and from acid deposition supplied from Taipei City. It is also derived from the oxidation of pyrite: the sulfur stable isotope ratios of delta 34S of +1@1000 to +4@1000 (relative to CDT) of sulfate in acid pond waters (pH 3-4) could be related to those of hydrogen sulfide in volcanic gas, pyrite in local pond sediments and soils, and sulfate in rain water. One acid source is sulfuric and hydrochloric acids arising in springs from geothermal activity: the delta 34S values were characterised by +13@1000 to +17@1000 sulfate-S, which was provided by a disproportionation reaction of sulfur dioxide in the depths. Another acid source could be the oxidation of iron(II). Under acidic conditions, the water-rock reaction gives rise to high concentrations of aluminium and iron. While flowing down surface streams, iron(II) is oxidised to iron(III) and then hydrolysed to cause further acidification under oxic conditions. The concentrations of iron and aluminium are controlled by redox and dissolution equilibria.     

Occurrence and behaviour of dissolved, nano-particulate and micro-particulate iron in waste waters and treatment systems: new insights from electrochemical analysis

Cyclic-, Differential Pulse- and Steady-state Microdisc Voltammetry (CV, DPV, SMV) techniques have been used to quantify the occurrence and fate of dissolved Fe(ii)/Fe(iii), nano-particulate and micro-particulate iron over a 12 month period in a series of net-acidic and net-alkaline coal mine drainages and passive treatment systems. Total iron in the mine waters is typically 10-100 mg L(-1), with values up to 2100 mg L(-1). Between 30 and 80% of the total iron occurs as solid phase, of which 20 to 80% is nano-particulate. Nano-particulate iron comprises 20 to 70% of the nominally "dissolved" (i.e. <0.45 μm) iron. Since coagulation and sedimentation are the only processes required to remove solid phase iron, these data have important implications for the generation or consumption of acidity during water treatment. In most waters, the majority of truly dissolved iron occurs as Fe(ii) (average 64 ± 22%). Activities of Fe(ii) do not correlate with pH and geochemical modelling shows that no Fe(ii) mineral is supersaturated. Removal of Fe(ii) must proceed via oxidation and hydrolysis. Except in waters with pH < 4.4, activities of Fe(iii) are strongly and negatively correlated with pH. Geochemical modelling suggests that the activity of Fe(iii) is controlled by the solubility of hydrous ferric oxides and oxyhydroxysulfates, supported by scanning and transmission electron microscopic analysis of solids. Nevertheless, the waters are generally supersaturated with respect to ferrihydrite and schwertmannite, and are not at redox equilibrium, indicating the key role of oxidation and hydrolysis kinetics on water treatment. Typically 70-100% of iron is retained in the treatment systems. Oxidation, hydrolysis, precipitation, coagulation and sedimentation occur in all treatment systems and - independent of water chemistry and the type of treatment system - hydroxides and oxyhydroxysulfates are the main iron sinks. The electrochemical data thus reveal the rationale for incomplete iron retention in individual systems and can thus inform future design criteria. The successful application of this low cost and rapid electrochemical method demonstrates its significant potential for real-time, on-site monitoring of iron-enriched waters and may in future substitute traditional analytical methods.     

Measuring reactive nitrogen emissions from point sources using visible spectroscopy from aircraft

Accurate measurements of nitrogen dioxide (NO2), a key trace gas in the formation and destruction of tropospheric ozone, are important in studies of urban pollution. Nitrogen dioxide column abundances were measured during the Texas Air Quality Study 2000 using visible absorption spectroscopy from an aircraft. The method allows for quantification of the integrated total number of nitrogen dioxide molecules in the polluted atmosphere and is hence a useful tool for measuring plumes of this key trace gas. Further, we show how such remote-sensing observations can be used to obtain information on the fluxes of nitrogen dioxide into the atmosphere with unique flexibility in terms of aircraft altitude, and the height and extent of mixing of the boundary layer. Observations of nitrogen dioxide plumes downwind of power plants were used to estimate the flux of nitrogen oxide emitted from several power plants in the Houston and Dallas metropolitan areas and in North Carolina. Measurements taken over the city of Houston were also employed to infer the total flux from the city as a whole.     

固定源排气中氮氧化物的测定

由于没有单独测定二氧化氮的方法标准、二氧化氮标准气体和测定二氧化氮便携式(电化学传感器)仪器标准,目前不能利用标准气体评价二氧化氮便携式(电化学传感器)仪器的性能;但是,可采用将NO2还原成NO后用化学发光法、非分散红外线法或电化学传感器法测定氮氧化物。     

Triethoxysilyl-substituted aminoethanethiol ligands for zinc and cadmium complexes and aminoethanethiol-modified silica gel. Evaluation of the corresponding supported molecular trap for metallic pollutant uptake (Cd2+, Hg2+ and Pb2+)

The reaction of 2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, a) and 1-methyl-2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, b) with ZnX2 and CdX2 (X = Cl, Br, I, NO3) in tetrahydrofuran (THF) or CH2Cl2 gives several complexes depending on the experimental conditions. Elemental analyses, IR, Raman, 13C[1H], 1H NMR and mass spectroscopies indicated the formation of mononuclear and dinuclear complexes. In the absence of NEt3 as proton quencher, the protonated ligands react in their zwitterionic form giving dinuclear [M(LH)X2]2 [M = Zn (1), Cd (2); LH = a, b; X = Cl, Br, I] or mononuclear M(NO3)2(LH)2 [M = Zn (5), Cd (6); LH = a] complexes. In both cases, coordination occurs through the S atoms, the ligands acting as terminal and bridging species. With NEt3, the deprotonated ligands are chelated through their N and S atoms and bridging occurs through the S atoms in [MLX]2 [M = Zn (3), Cd (4); LH = a; X = Cl, Br] complexes. The LH ligand is chemically grafted onto silica, the procedure optimized and the resulting material characterized by 13C and 29Si cross-polarization, magic-angle spinning (CP-MAS) NMR and DRIFT. This material is evaluated as a supported molecular trap for binding heavy metals (Cd2+, Hg2+, Pb2+) in aqueous solution. In both batch and column processes, it appears that Hg2+ and Pb2+ are trapped more than Cd2+, but in all cases values lower than those allowed were obtained.     

Short-term Emissions of Ammonia and Carbon Dioxide from Cattle Urine Contaminated Tropical Grassland Microcosm

The study was designed to understand the emissions of ammonia (NH₃) and carbon dioxide (CO₂) from a single cattle urination event on a tropical grassland and underline the significance of the emissions in the context of huge animal population grazing on large pasture areas in some countries. Emissions of ammonia (NH₃) and carbon dioxide (CO₂) were monitored for three weeks from a tropical grassland (dominated by Cynodon dactylon Pers.) microcosm contaminated with cow and buffalo urine. The grassland microcosms were treated with urine (50 and 100 ml of each) only once and irrigated with water once every week. Ammonia was sampled by an automatic sampling system comprising of a vacuum pump, three-way stopcocks and rubber tubing and an impinger containing suitable absorbing solution (H₂SO₄), connected to the tubing suitably. The sampled gas, after sucked by the vacuum pump and absorbed in H₂SO₄, was allowed to enter the closed microcosm again maintaining internal pressure of the microcosm. Carbon dioxide was sampled by absorption in an alkali (NaOH) trap inside the microcosm. Both NH₃ and CO₂ emissions were highly variable temporally and there was no continuous increasing or decreasing emission trend with time. Respectively, 45 and 46% of total NH₃-N were emitted within first 48 h from 50 and 100 ml cow urine application while the corresponding values for buffalo urine were 34 and 32%. Total NH₃-N emissions, integrated for sampling days (i.e. 1, 2, 3, 4, 6, 15, 18 and 21st) were 11 and 6% in cow and 8 and 5% in buffalo urine, of the total-N added through 50 and 100 ml urine samples. Carbon dioxide emissions were standardized at 25 ^∘C by using a suitable formula which were lower than actual emissions at actual soil temperature (> 25 ^∘C). Carbon dioxide emission rates were classified on the basis of soil repiratory classification and classes ranged from moderately low soil activity up to unusually high soil activity, the latter observed only on very few sampling days. Grasses in the microcosm had shown appreciable growth after urine application. Although variable and somewhat unpredictable, emissions were appreciable and that too only from a patch of single urination, indicating to the huge magnitude of total emissions under the scenario of thousands of cattle grazing on hundreds of acres of grasslands in a tropical country.     

基于环境库兹涅茨曲线特征的桂林市大气环境状况研究

根据2006年-2012年桂林市经济发展主要指标和大气环境污染指标的统计资料,分析了该市人均 GDP 与SO2、NO x、烟（粉）尘排放量及 PM10质量浓度和 API优良率等大气环境指标的相关关系,建立了经济发展与大气环境指标之间的模拟曲线。模拟结果表明,桂林市处于工业时期,随着人均GDP增加,SO2和烟（粉）尘排放得到了一定程度的缓解,而NO x 和 PM10排放从长期看还处于上升趋势。建议改善能源结构,调整产业结构和工业布局,制定财税激励政策,开展环境综合整治,加大机动车排污防治力度,进一步控制大气污染。     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

Reducing dust exposure in indoor climbing gyms

As users of indoor climbing gyms are exposed to high concentrations (PM(10) up to 4000 μg m(-3); PM(2.5) up to 500 μg m(-3)) of hydrated magnesium carbonate hydroxide (magnesia alba), reduction strategies have to be developed. In the present paper, the influence of the use of different kinds of magnesia alba on dust concentrations is investigated. Mass concentrations, number concentrations and size distributions of particles in indoor climbing gyms were determined with an optical particle counter, a synchronized, hybrid ambient real-time particulate monitor and an electrical aerosol spectrometer. PM(10) obtained with these three different techniques generally agreed within 25%. Seven different situations of magnesia alba usage were studied under controlled climbing activities. The use of a suspension of magnesia alba in ethanol (liquid chalk) leads to similar low mass concentrations as the prohibition of magnesia alba. Thus, liquid chalk appears to be a low-budget option to reduce dust concentrations. Magnesia alba pressed into blocks, used as powder or sieved to 2-4 mm diameter, does not lead to significant reduction of the dust concentrations. The same is true for chalk balls (powder enclosed in a sack of porous mesh material). The promotion of this kind of magnesia alba as a means of exposure reduction (as seen in many climbing gyms) is not supported by our results. Particle number concentrations are not influenced by the different kinds of magnesia alba used. The particle size distributions show that the use of magnesia alba predominantly leads to emission of particles with diameters above 1 μm.     

Seasonal characteristics of SO2, NO2, and CO emissions in and around the Indo-Gangetic Plain

Anthropogenic emissions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and carbon monoxide (CO) exert significant influence on local and regional atmospheric chemistry. Temporal and spatial variability of these gases are investigated using surface measurements by the Central Pollution Control Board (India) during 2005–2009 over six urban locations in and around the Indo-Gangetic Plain (IGP) and supported using the satellite measurements of these gases. The stations chosen are Jodhpur (west of IGP), Delhi (central IGP), Kolkata and Durgapur (eastern IGP), Guwahati (east of IGP), and Nagpur (south of IGP). Among the stations studied, SO₂ concentrations are found to be the highest over Kolkata megacity. Elevated levels of NO₂ occur over the IGP stations of Durgapur, Kolkata, and Delhi. Columnar NO₂ values are also found to be elevated over these regions during winter due to high surface concentrations while columnar SO₂ values show a monsoon maximum. Elevated columnar CO over Guwahati during pre-monsoon are attributed to biomass burning. Statistically significant correlations between columnar NO₂ and surface NO₂ obtained for Delhi, Kolkata, and Durgapur along with very low SO₂ to NO₂ ratios (≤0.2) indicate fossil fuel combustion from mobile sources as major contributors to the ambient air over these regions.     

Emission rate formulae for surface iron ore mining activities

A study was carried out at three surface iron ore mines to determine the total suspended particulate emission rate and to develop the formula for the emission rate of various surface iron ore mining activities. The study covered various mining activities and locations including waste loading and unloading, iron ore loading and unloading, screening plant, exposed waste dump, stock yard, exposed pit surface, transport road and haul road. A set of 10 formulae was developed to calculate the total suspended particulate emission rate of various surface iron ore mining activities. The emission of gaseous pollutants (sulphor dioxide and oxides of nitrogen) was also evaluated but was found negligible for various mining activities, and emission rates were determined for overall mine only. The developed formulae were validated with the measured emission data at another surface iron ore mine. The accuracy of the activity-wise emission rates calculated using the developed formulae was found to vary from 92 to 97% of actual field measurement data. The developed formulae for determination of emission rate from various surface iron ore mining activities will help in predicting air quality status through air quality modelling and designing effective mitigative measures for sensitive areas during the planning stage of a proposed mine.