废铅酸蓄电池铅膏铵法预脱硫过程的动力学分析

以废铅酸蓄电池中铅膏为研究对象,开展了用NH_4HCO_3为脱硫剂对铅膏进行脱硫转化的实验研究。通过分析反应过程中PbSO_4转化率随时间的变化关系,考察了搅拌速度、反应温度及NH_4HCO_3浓度对铅膏脱硫转化的影响;利用固液多相反应的收缩核模型,分析了反应的动力学过程,并计算了反应的表观活化能及表观反应级数。结果表明:在实验选取的条件范围内,提高反应温度、增大NH_4HCO_3浓度及加快搅拌速度均可以促进铅膏的脱硫转化;表观活化能为9.7 kJ·mol~(-1),表观反应级数为0.71,反应过程受内扩散步骤控制。研究结果可为铅膏铵法预脱硫技术能高效、低耗的应用提供参考。     

磺胺类制药废水中苯系物的快速同步检测

磺胺类制药废水是一类难降解有机废水,其中含有苯磺酰胺、苯磺酸、苯酚等苯系物,对这些物质的快速检测十分必要,针对这3种物质建立了基于高效液相色谱的快速同步检测方法。采用C18柱为分离柱,比较了乙腈/水、甲醇/水和甲醇/缓冲盐3种流动相体系的分离效果,优化了230、240、250和260 nm 4种检测波长等条件。结果表明,V甲醇∶V磷酸二氢铵溶液(0.5%,p H=3.5)=50∶50作为流动相时,基线稳定,峰形较好,3种目标物在11 min内即可实现有效分离,且浓度为5～100 mg·L~(-1)时,3种目标物峰面积与质量浓度的线性关系良好(R20.999),检出限为15.0～29.4μg·L~(-1),相对偏差为0.05%～1.56%(n=5),该方法能同时检测苯磺酸、苯酚和苯磺酰胺,具有简便、灵敏、准确等优点,可为制药废水的快速检测和磺胺类药物降解机理的分析提供便利。     

二噁英类物质CALUX报告基因法在造纸行业的应用探究

选择典型造纸厂,采用化学激活报告基因法(CALUX)测定造纸过程中废水和纸浆中的二噁英类物质,并将部分样品测定结果与高分辨气相色谱-高分辨质谱(HRGC-HRMS)法测定结果作线性回归,换算系数为0.21,表明CALUX可用于造纸行业废水中二噁英类物质的快速筛查。将CALUX用于测定造纸厂废水中二噁英类物质,结果表明用含元素氯的漂白工艺会产生大量二噁英类物质,其中漂白废水中的目标物毒性当量浓度最高,经处理后可达到国家排放标准;而用无元素氯的漂白工艺,二噁英类物质的产生量会大幅降低。     

Point Sampling Digital Imagery with ‘Samplepoint’

Measuring percent occurrence of objects from digital images can save time and expense relative to conventional field measurements. However, the accuracy of image analysis had, until now, not reached the level of the best conventional field measurements. Additionally, most image-analysis software programs require advanced user training to successfully analyze images. Here we present a new software program, ‘SamplePoint,’ that provides the user a single-pixel sample point and the ability to view and identify the pixel context. We found SamplePoint to allow accuracy comparable with the most accurate field-methods for ground-cover measurements. Expert use of the program requires minimal training and its ease of use allows rapid measurements from image data. We recommend SamplePoint for calibrating the threshold-detection level of image-analysis software or for making direct measurements of percent occurrence from digital images.     

Can we gain precision by sampling with probabilities proportional to size in surveying recent landscape changes in the Netherlands?

Seventy-two squares of 100 ha were selected by stratified random sampling with probabilities proportional to size (pps) to survey landscape changes in the period 1996–2003. The area of the plots times the urbanization pressure was used as a size measure. The central question of this study is whether the sampling with probabilities proportional to size leads to gain in precision compared to equal probability sampling. On average 1.03 isolated buildings per 100 ha have been built, while 0.90 buildings per 100 ha have been removed, leading to a net change of 0.13 building per 100 ha. The area with unspoiled natural relief has been reduced by 2.3 ha per 100 ha, and the length of linear relicts by 137 m per 100 ha. On average 74 m of linear green elements have been planted per 100 ha, while 106 m have been removed, leading to a net change of −31 m per 100 ha. For the state variables ‘unspoiled natural relief', ‘ linear relicts', ‘removed linear green elements', and ‘new – removed linear green elements' there is a gain in precision due to the pps-sampling. For the remaining state variables there is no gain or even a loss of precision (`new buildings', ‘removed buildings', ‘new – removed buildings', ‘new linear green elements'). Therefore, if many state variables must be monitored or when interest is not only in the change but also in the current totals, we recommend to keep things simple, and to select plots with equal probability.     

Characterization of Benthic Communities and Physical Habitat in the Stanislaus, Tuolumne, and Merced Rivers, California

The primary goal of this study was to characterize physical habitat and benthic communities (macroinvertebrates) in the Stanislaus, Tuolumne and Merced Rivers in California’s San Joaquin Valley in 2003. These rivers have been listed as impaired water bodies (303 (d) list) by the State of California due to the presence of organophosphate (OP) insecticides chlorpyrifos and diazinon, Group A pesticides (i.e., organochlorine pesticides), mercury, or unknown toxicity. Based on 10 instream and riparian physical habitat metrics, total physical habitat scores in the Stanislaus River ranged from 124 to 188 (maximum possible total score is 200). The highest total habitat score was reported at the upstream site. Tuolumne River physical habitat scores ranged from 86 to 167. Various Tuolumne River physical habitat metrics, including total habitat score, increased from downstream to upstream in this river. Merced River physical habitat scores ranged from 121 to 170 with a significant increase in various physical habitat metrics, including total habitat score, reported from downstream to upstream. Channel flow (an instream metric) and bank stability (a riparian metric) were the most important physical habitat metrics influencing the various benthic metrics for all three rivers. Abundance measures of benthic macroinvertebrates (5,100 to 5,400 individuals) were similar among the three rivers in the San Joaquin watershed. Benthic communities in all three rivers were generally dominated by: (1) Baetidae species (mayflies) which are a component of EPT taxa generally considered sensitive to environmental degradation; (2) Chironomidae (midges) which can be either tolerant or sensitive to environmental stressors depending on the species; (3) Ephemerellidae (mayflies) which are considered sensitive to pollution stress; and (4) Naididae (aquatic worms) which are generally considered tolerant to environmental stressors. The presence of 117 taxa in the Stanislaus River, 114 taxa in the Tuolumne River and 96 taxa in the Merced River implies that the benthic communities in these streams are fairly diverse but without a clear definition of benthic community expectations it is unknown if these water bodies are actually impaired.     

Spatial and Temporal Variations in Trace Metal Concentrations in the Cockle, Austrovenus Stutchburyi from Otago, New Zealand

This is the first comprehensive study of sources of variation in metal concentrations within the whole tissues of a shallow burrowing, filter-feeding intertidal clam, Austrovenus stutchburyi. Samples were collected from 12 sites in April, August, November and February in 1993–1994 in the vicinity of Otago Harbour and Peninsula, New Zealand. Total tissue trace metal concentrations (μg g⁻¹ dry weight) were measured in individual animals for the essential metals : Mn, Cu, Zn, Ni and the non-essential Cr using trace-metal clean acid-digestion and ICP-OAES techniques. Average metal concentrations were 3–60 μg g⁻¹ for Cu, 40–118 μg g⁻¹ for Zn, 2–12 μg g⁻¹ for Mn, 5–35 μg g⁻¹ for Ni and 1–44 μg g⁻¹ for Cr. These levels decreased with body weight and differed amongst sites except for Cr in February (mid-summer). Highest concentrations occurred at sites close to a city (Dunedin) and within the central harbour region although the Cu, Zn, Ni and Cr concentrations did not correlate with the environmental gradient or season. At one coastal site, samples of both the blue mussel Mytilus galloprovincialis and cockles gave similar trends in trace metal levels. These results suggest that the cockle could be a useful trace metal biomonitor within NZ estuaries.     

Comparison of 24 h averaged VOC monitoring results for residential indoor and outdoor air using Carbopack X-filled diffusive samplers and active sampling--a pilot study

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.     

Preparation of 2-mercaptobenzothiazole-derivatized mesoporous silica and removal of Hg(ii) from aqueous solution

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second reaction a multifunctionalized N,S donor compound (2-mercaptobenzothiazol) was incorporated to obtain the functionalized silicas denoted as MBT-SBA-15-Het and MBT-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MBT-SBA-15-Hom or MBT-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions at pH 6 contaminated with Hg(ii) at room temperature. Results obtained indicate that mercury adsorption was higher in the mesoporus silicas prepared by the homogeneous method, and the maximum adsorption value (0.24 +/- 0.02 mmol Hg(ii) g(-1)) was obtained for MBT-SBA-15-Hom. The chemically stability in acid medium of the functionalized silicas, possibility its regeneration washing with concentrate HCl, resulting in the reuse of the adsorbent material for several cycles.     

Status of the Riparian Ecosystem in the Upper San Pedro River, Arizona: Application of an Assessment Model

A portion of Arizona’s San Pedro River is managed as a National Riparian Conservation Area but is potentially affected by ground-water withdrawals beyond the conservation area borders. We applied an assessment model to the Conservation Area as a basis for monitoring long-term changes in riparian ecosystem condition resulting from changes in river water availability, and collected multi-year data on a subset of the most sensitive bioindicators. The assessment model is based on nine vegetation bioindicators that are sensitive to changes in surface water or ground water. Site index scores allow for placement into one of three condition classes, each reflecting particular ranges for site hydrology and vegetation structure. We collected the bioindicator data at 26 sites distributed among 14 reaches that had similar stream flow hydrology (spatial flow intermittency) and geomorphology (channel sinuosity, flood-plain width). Overall, 39% of the riparian corridor fell within condition class 3 (the wettest condition), 55% in condition class 2, and 6% in the driest condition class. Condition class 3 reaches have high cover of herbaceous wetland plants (e.g., Juncus and Schoenoplectus spp.) along the perennial stream channel and dense, multi-aged Populus-Salix woodlands in the flood plain, sustained by shallow ground water in the stream alluvium. In condition class 2, intermittent stream flows result in low cover of streamside wetland herbs, but Populus-Salix remain abundant in the flood plain. Perennial wetland plants are absent from condition class 1, reflecting highly intermittent stream flows; the flood plain is vegetated by Tamarixa small tree that tolerates the deep and fluctuating ground water levels that typify this reach type. Abundance of herbaceous wetland plants and growth rate of Salix gooddingii varied between years with different stream flow rates, indicating utility of these measures for tracking short-term responses to hydrologic change. Repeat measurement of all bioindicators will indicate long-term trends in hydro-vegetational condition.