有效磷含量对硝酸铵溶液热安全性的影响

为了了解硝酸磷肥生产过程中,硝酸铵溶液中加入磷酸一铵的安全性,通过自制实验装置,研究了有效磷含量对质量分数为85%的硝酸铵溶液热分解的影响。结果表明,质量分数为85%的硝酸铵和磷酸一铵混合溶液的临界爆炸温度高于纯质量分数为85%的硝酸铵溶液,稳定性更好;磷酸一铵抑制硝酸铵的热分解,随着有效磷含量的增加,硝酸铵混合溶液临界爆炸温度升高;升温速率对硝酸铵混合溶液的临界爆炸温度影响很大,随着升温速率由2℃/min升高到3℃/min,质量分数为85%的硝酸铵混合溶液的临界爆炸温度升高,不易发生爆炸,安全性更好。研究结果对硝酸磷肥的生产安全有一定的指导意义。     

Effect of urea on detonation characteristics and thermal stability of ammonium nitrate

A study has examined the effect of urea on the thermal stability and detonation characteristics of ammonium nitrate (AN). The thermal decomposition temperature and surface morphology of samples were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). For further research on the thermal sensitivity and shock sensitivity of the samples, the Koenen test and UN gap test were conducted. The results indicate that urea can substantially increase the thermal stability of AN (the greatest exothermic peak is increased by more than 100 °C) and reduce the thermal sensitivity of AN. However, AN-50wt. % urea mixtures can still produce a steady detonation in the UN gap test. Urea cannot reduce the ability to propagate a detonation. Possible explanations for these results are discussed.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

典型河谷城市儿童土壤与灰尘铅暴露风险

为定量评价河谷型城市土壤与灰尘铅对城市儿童健康的影响与风险,结合野外调查的基础上,以陕西渭河谷地典型工业城市宝鸡、西安、渭南和铜川为研究区域,以定量分析河谷型城市儿童环境铅暴露为核心,收集4个城市土壤与灰尘分析样品总计243个。利用X射线荧光光谱法测定了4个城市土壤与灰尘铅的含量;采用BCR连续形态分级法探究了城市土壤与灰尘重金属铅地球化学形态分布与迁移特征;根据US EPA污染物暴露与健康风险评价模型对城市儿童铅暴露进行了评价。研究结果表明渭河谷地典型城市宝鸡、铜川、西安和渭南城市土壤与灰尘铅浓度(X±SD)分别为(409.2±52.54)和(624.70±66.15)mg·kg-1、(357.47±41.37)和(592.60±36.78)mg·kg-1、(61.4±13.31)和(78.42±14.89)mg·kg-1、(46.71±12.11)和(64.7±13.76)mg·kg-1,均高出陕西省土壤铅背景值;污染水平依次为宝鸡铜川西安渭南。4个河谷型城市土壤与灰尘重金属铅发生整体迁移的趋势为:宝鸡城市灰尘(90.71%)西安城市灰尘(84.74%)≥宝鸡城市土壤(83.12%)渭南城市灰尘(74.89%)≥西安城市土壤(74.50%)铜川城市灰尘(72.49%)铜川城市土壤(57.50%)渭南城市土壤(53.79%)。可见,铅在均在城市灰尘中的迁移趋势远大于相应的城市土壤。4个城市土壤与灰尘均表现出较大的儿童暴露致癌风险,宝鸡和铜川城市儿童土壤与灰尘铅暴露也分别存在非致癌风险,风险程度依次为宝鸡铜川西安渭南。儿童铅暴露致癌与非致癌风险程度与其城市土壤和灰尘中铅可氧化态分布呈相似的规律,表明碱性的城市土壤与城市灰尘(p H7)中可氧化态铅可能是导致河谷型城市儿童铅暴露风险和儿童血铅污染的主要形态和因素。由此,城市燃煤排放与含铅制品的加工等活动可能是渭河谷地河谷型城市儿童血铅与铅暴露最主要的贡献源,必须采取长期有效的监测与控制措施。     

Evaluating farm performance using agri-environmental indicators: recent experiences for nitrogen management in The Netherlands

Intensive agriculture, characterized by high inputs, has serious implications on the environment. Monitoring and evaluation of projects aiming at designing, testing and applying more sustainable practices require instruments to asses agronomic as well as environmental performance. Guidelines for Good Agricultural Practice (GAP) or Good Farming Practice (GFP) define sustainable practices but give limited insight into their environmental performance. Agri-environmental indicators (AEIs) provide information on environmental as well as agronomic performance, which allows them to serve as analytical instruments in research and provide thresholds for legislation purposes. Effective AEIs are quantifiable and scientifically sound, relevant, acceptable to target groups, easy to interpret and cost-effective. This paper discusses application of four AEIs for nitrogen (N) management in three Dutch research projects: 'De Marke', 'Cows and Opportunities' and 'Farming with a future'. 'De Marke' applied Nitrogen Surplus and Groundwater Nitrate Concentration in the design and testing of environmentally sound dairy systems. 'Cows and Opportunities', testing and disseminating dairy systems designed at 'De Marke', mainly applied Nitrogen Surplus, while 'Farming with a future' used Nitrogen Surplus, Groundwater Nitrate Concentration and Residual Mineral Soil Nitrogen to support arable farmers in complying with Dutch legislation (MINAS). Nitrogen Surplus is quantifiable, appealing and easy to interpret, but lacks scientific soundness or a good relationship with groundwater quality. Nitrogen Use Efficiency is sensitive to changes in management, while Residual Mineral Soil Nitrogen is appealing and cheap, but has difficulties in scaling. Groundwater Nitrate Concentration lacks clear rules for sampling, is labor consuming, expensive and mainly used in combination with other indicators. AEIs enhanced improvements in N management by facilitating (i) definition of project goals, (ii) design of desired systems, (iii) evaluation of applied systems and (iv) improving effective communication. AEI applications in other countries show a similar pattern as found in The Netherlands. Limitations to AEI application relate to inconsistencies between different indicators, heterogeneity of soil characteristics and linkages of N, carbon and water management. AEIs should be applied in an integrated evaluation, at a scale that reflects the farm's spatial variability. Simple AEIs like Nitrogen Surplus should be supported by other indicators and/or model calculations. The paper concludes that AEIs proved their value in design, implementation and testing of farming systems, but they should be used with care, always keeping in mind that indicators are simplifications of complex and variable processes.     

不同磁黄铁矿自养反硝化脱氮除磷作用

氮磷排放标准日趋严格,开发高效廉价脱氮除磷材料已成为研究热点.采用黄铁矿与赤铁矿在管式炉中氮气气氛下600 ℃煅烧,得到硫化赤铁矿形成的磁黄铁矿、黄铁矿热分解形成的磁黄铁矿,构建磁黄铁矿-方解石体系处理含氮磷模拟废水,对比不同方式制备的磁黄铁矿、天然磁黄铁矿、黄铁矿、硫磺脱氮除磷性能,考察不同磁黄铁矿晶体结构和结晶度差异及其对脱氮除磷影响,探究不同体系中矿物结构和微生物群落变化.结果表明：黄铁矿热分解产物以六方磁黄铁矿为主;硫化赤铁矿产物以低结晶度的单斜磁黄铁矿为主,因而表现出优异的脱氮除磷活性,氮磷去除率分别为99.8%和96.8%.铁硫化物与微生物反应产物的XRD、SEM和FE-TEM分析结果表明,微生物能有效利用磁黄铁矿进行脱氮,磷酸盐主要以FePO₄形式被去除.群落分析结果表明铁硫化物脱氮除磷体系中的主要功能菌属为Thiobacillus和 Sulfurimonas,结晶度低的单斜磁黄铁矿更有利于Thiobacillus定向富集.     

基于拉曼光谱的铅致肝细胞生物分子变化研究

利用拉曼光谱技术采集不同铅离子暴露时间(0.5,1.5,3,6,12,24h)、暴露浓度(0.05,0.1,0.5,1,5mg/L)下HepG2细胞的光谱数据,欲探究在不同铅暴露条件下肝细胞的分子变化及其相关机制.研究结果发现,在不同条件下各组细胞的光谱形态基本相同,但部分特征峰的吸光度强度存在差异.经多元统计分析发现,除6h外,同一暴露时间下不同暴露浓度细胞的光谱数据在LD1上均存在离散趋势,并在暴露24h时最明显.细胞内蛋白质、脂质、核酸、类胡萝卜素、碳水化合物等生物分子的特征峰表现出明显差异,但不同类型生物分子发生显著变化的时间并不相同.由此可见铅暴露可损伤肝细胞蛋白质、脂质、核酸、类胡萝卜素的结构并影响其正常功能,这种毒性效应呈剂量-效应关系,且随暴露时间的增加而增加.本研究说明拉曼光谱可以实现铅对肝细胞生物分子变化的相关检测,这不仅为之后的细胞毒理研究提供了新的思路,同时也为环境污染物的安全评价提供了理论依据.     

Estimation of Nonpoint Source Nitrate Concentrations in Indiana Rivers Based on Agricultural Drainage in the Watershed

Subsurface tile‐drained agricultural fields are known to be important contributors to nitrate in surface water in the Midwest, but the effect of these fields on nitrate at the watershed scale is difficult to quantify. Data for 25 watersheds monitored by the Indiana Department of Environmental Management and located near a U.S. Geological Survey stream gage were used to investigate the relationship between flow‐weighted mean concentration (FWMC) of nitrate‐N and the subsurface tile‐drained area (DA) of the watershed. The tile DA was estimated from soil drainage class, land use, and slope. Nitrate loads from point sources were estimated based on reported flows of major permitted facilities with mean nitrate‐N concentrations from published sources. Linear regression models exhibited a statistically significant relationship between annual/monthly nonpoint source (NPS) nitrate‐N and DA percentage. The annual model explained 71% of the variation in FWMC of nitrate‐N. The annual and monthly models were tested in 10 additional watersheds, most with absolute errors within 1 mg/l in the predicted FWMC. These models can be used to estimate NPS nitrate for unmonitored watersheds in similar areas, especially for drained agricultural areas where model performance was strongest, and to predict the nitrate reduction when various tile drainage management techniques are employed.     

Management of used lead acid battery in China: Secondary lead industry progress,policies and problems

The amount of used lead acid batteries rises along with the rapid development of battery manufacture in China. The battery manufacture and recycling industry has developed sharply in these recent 5 years. The annual production of secondary lead from used lead acid batteries in China increased rapidly to 1.5 million tonnes (MT) in 2013, making china the world's largest secondary lead producer. Secondary lead enterprises are mainly located in the middle and eastern regions of China, with a legal production capacity of 3 MT/year. Environmental pollution problems began to happen frequently from 2009. After 2011, the government began to put in efforts to promote pollution control, eliminate outdated production capacity, support advanced production and technology innovation research, and has achieved remarkable results. However, the main existing problems are that the proportion of secondary lead production is only 30% of the total lead production, no formal recycling network has been established and the overall level of industrial technology and equipment is outdated. Compared with developed countries, this paper predicts that, secondary proportion will reach 44% in 2015 and 60% in 2028. Finally some countermeasures are given to the recycling mode and technology promotion.     

江苏省铅蓄电池行业环保现状及对策

近年来铅蓄电池行业血铅污染事件引发了社会各界群众的高度关注,国家和地方也陆续颁布和实施了一系列控制重金属污染的法规政策,将铅蓄电池行业推向了改革的风口浪尖。经过几年的初步改革,虽然相关企业的环保行为有所提升,但与国家和地方的要求仍存在不小差距。以江苏省现有规模以上铅蓄电池生产企业为研究对象,深入剖析各企业在环境保护方面存在的突出问题,有针对性的提出环保发展对策,为全省乃至全国铅蓄电池行业的综合整治和产业升级指明方向,具有重要的现实意义。