Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PC_n, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg⁻¹ dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PC_n, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg ⁻¹ EDTA, vetiver accumulated 4460 and 480 mg Pb kg⁻¹ dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC₁) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC₁-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.     

Screening analysis of volatile organic contaminants in commercial inorganic coagulants used for drinking water treatment

A method for quality screening is suggested to detect volatile impurities in inorganic coagulants that are used for drinking water treatment. Static headspace gas chromatography with mass spectrometry detection (HS–GCMS) is sensitive and selective to detect volatiles in low concentrations. This study has discovered that volatile organic impurities are detectable in ferric and aluminium-based coagulants which are used for drinking water treatment. For ferric chloride, 2-propanol was detected at a level of 17–24 μg ml⁻¹, acetone at 0.7–1.7 μg ml⁻¹, 1,1,1-trichloroacetone at 0.02–0.04 μg ml⁻¹, trichloromethane at 0.01–0.02 μg ml⁻¹ and toluene at 0.01–0.12 μg ml⁻¹. For ferric chloride sulfate, acetone was detected at a level of 0.12 μg ml⁻¹, 1,1,1-trichloroacetone at 0.06–0.08 μg ml⁻¹, trichloromethane at 0.13–0.23 μg ml⁻¹, bromodichloromethane at 0.04–0.06 μg ml⁻¹ and dibromochloromethane at 0.04–0.05 μg ml⁻¹. For aluminium hydroxide chloride, only trichloromethane was detectable, but below the method detection limits (MDL). Although the concentrations of these impurities in commercial coagulants are low, this observation is important and should have impact on water industries for them to pay attention to the chemicals they are using for drinking water production.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

单柱阳离子色谱快速分析白云石中高含量钙镁

采用离子色谱法同时测定白云石中高含量钙镁,该法与目前使用的络合滴定法相比,具有准确可靠、操作简便快速、无干扰等特点。对样品测定取得了满意的结果,氧化钙与镁瓣含量分别为３１．９９％和２１．４７％,相对标准偏差分别为０．８１％和０．６５％,平均回收率分别９９．９％和１０２％。     

宁波市饮用水源地爆发蓝藻水华时微囊藻毒素的污染分析

通过固相萃取净化,建立了超高效液相色谱-串联四极杆质谱法测定水中微囊藻毒素MC-LR和MC-RR的方法,并用该方法监测了宁波市两个饮用水源地爆发蓝藻水华时水体中的微囊藻毒素.监测结果表明,姚江水体中的微囊藻毒素污染水平低,MC-LR和MC-RR没有被检出;梅湖水库水体中MC-RR也未被检出,采取措施后,虽MC-LR有时被检出,但最高时也低于国家标准值(1.0μg/L).     

生化需氧量测定的方法改进

生化需氧量测定中接种液的制备和稀释倍数的确定是2个关键的步骤,本文提出一种可行的制备接种液的方法,根据实践经验,总结出一种稀释倍数计算方法,适合在实际分析中使用。     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

碳包覆Pd/Al2O3催化剂催化4-溴苯酚加氢脱溴的活性和稳定性调控研究

在污染物液相催化加氢脱卤过程中,提高催化剂的稳定性至关重要.以水热合成法制备了不同碳包覆量的Pd/Al₂O₃@C催化剂,对催化剂进行了系列表征,并将催化剂应用于4-溴苯酚(4-BP)污染物的催化加氢脱溴反应.表征结果显示碳层提高了Pd/Al₂O₃的表面疏水性,有利于4-BP在催化剂上的吸附.并且在Pd/Al₂O₃@C催化剂的碳化过程中,碳还原部分Pd颗粒,并保留部分正价态Pd活性位,增强了4-BP中C-Br键的活化.与Pd/Al₂O₃相比,碳涂层提高了催化剂的催化活性.但当碳包覆量超过最佳包覆量后,暴露的Pd粒子随碳包覆量的增加而减少,导致活性下降.此外,碳层修饰后,催化剂的稳定性显著提高,从而大大抑制了Pd粒子的团聚和损耗.Pd/Al₂O₃@C表面的碳涂层对卤素具有较高的耐受性,从而减轻了液相催化加氢脱卤反应中活性中心的中毒.     

云南曲靖某煤化工基地及周边土壤中多环芳烃的检测研究

采用快速溶剂提取处理土壤样品,利用气相色谱质谱内标法测定土壤中多环芳烃,其检出限范围为2.01~3.68μg/kg,相对标准偏差为2.6%~14.7%,加标回收率为67.1%~119%。结果表明,此方法具有良好的灵敏度、准确度和精密度。本研究对11个不同采样点土壤进行了检测分析,并考察了土壤中多环芳烃的污染水平。     

碱片-离子色谱法测定硫酸盐化速率影响因素

采用碱片-离子色谱法测定空气的硫酸盐化速率,方法在硫酸盐质量浓度为1.00~20.0 mg/L范围内线性良好(r≥0.999 0);碱片剪碎或不剪碎对空白碱片中硫酸根离子质量浓度的测定无明显影响,且高低两种加标浓度的回收率均在80.0%~120%之间;对于碱片实际样品,碱片剪碎更有利于硫酸根离子的快速溶出;随浸泡时间的延长,碱片中溶出的硫酸根离子质量浓度呈上升趋势,7 h硫酸根离子基本溶出完全,从保证结果质量和节省时间的角度考虑,确定最佳浸泡时间为3.5 h,建议碱片全部采取剪碎处理。