贵阳市城区PM10和PM2.5水溶性离子特征分析

分别于2013年10月和2014年2月、5月、7月在贵阳市城区3个环境空气质量监测国控点位（南明区市监测站、云岩区黔灵公园马鞍山和观山湖区贵阳一中）进行PM₁₀、PM_2.5样品采集，并对10种水溶性离子（SO₄^2-、NO₂^-、NO₃^-、NH₄⁺、Cl^-、F^-、Na⁺、K⁺、Mg²⁺、Ca²⁺）的含量进行了分析。结果表明，研究时段内，贵阳市3个点位PM₁₀、PM_2.5平均质量浓度分别为（64.8±25.5）、（46.6±21.2）μg/m³。其中，云岩区黔灵公园马鞍山点位的颗粒物浓度最低，南明区市监测站点位最高。3个点位PM_2.5平均浓度与PM₁₀平均浓度的比值为0.719，表明贵阳市城区PM₁₀中，PM_2.5占主导地位。水溶性离子分析显示，SO₄^2-、NO₂^-、NO₃^-、NH₄⁺、Cl^-、F^-、Na⁺、K⁺主要分布在PM_2.5中，Mg²⁺、Ca²⁺主要分布在PM₁₀中。3个点位PM₁₀和PM_2.5中的水溶性离子均表现为SO₄^2-、NH₄⁺、Ca²⁺浓度较大，F^-、NO₂^-较小，表明3个点位的污染源总体相同，且水溶性离子占PM₁₀、PM_2.5含量的比例达33.6%~48.1%。贵阳市城区大气中的SO₂转化率在5月、7月、10月较高，2月最低，主要是由于5月、7月、10月的高温、高湿、强辐射环境条件促进了SO₂向SO₄^2-的转化。阴阳离子平衡分析表明，贵阳市城区PM₁₀、PM_2.5呈现出偏碱性的特征。水溶性离子主成分分析表明，贵阳市城区PM₁₀中的水溶性离子主要来源于城市扬尘、生物质燃烧尘、煤烟尘、建筑尘以及二次粒子，PM_2.5中水溶性离子的来源与PM₁₀较为相似。     

Hydrochemistry of drinking water sources and water purifiers in relation to epidemiological study in Hisar,North-West India

The concern related to the drinking of reverse osmosis (RO) water containing low levels of minerals is growing day by day. This study involves the analysis of water samples from various drinking water sources in a rural site, Mirchpur village, an Indus Valley civilization site (grid location: 29° 18′ 42.3″ N, 76° 10′ 33.0″ E) of Hisar, India, along with the health survey of human subjects. The hydrochemistry of water collected from hand pumps, river canals, tube wells, submersibles, and the RO systems installed in various homes was explored for pH, EC, TH, TDS, turbidity, cations (Na⁺, Ca²⁺, Mg²⁺), anions (CO₃²⁻, HCO₃⁻, Cl⁻, SO₄²⁻, NO₃⁻, F⁻), and elements (Fe, Pb, Se) employing the ion chromatography, flame photometry, and ICP-AES techniques. Lead (Pb) and Selenium (Se) were detected in trace amounts (0.30–2.6 μg L⁻¹; 0.10–4.1 μg L⁻¹, respectively) in all the samples, including the samples collected from RO purifiers, but Iron (Fe) was not detected in RO samples even in trace amounts. The F-levels in hand pump water (HPW) and submersible water (SW) (1.9  and 1.7 mg L⁻¹, respectively) and TDS levels in SW (3048 mg L⁻¹) were found to be above WHO and BIS safe limits. TDS levels in the river canal (900 mg L⁻¹), tube well (1104 mg L⁻¹), hand pump (1170 mg L⁻¹), and submersible samples (3048 mg L⁻¹) were found significantly higher as compared to the RO personal water (ROPW; 216 mg L⁻¹) and RO supply water (ROSW; 90 mg L⁻¹). The collected epidemiological data reveals that 21%, 19%, 13%, and 12% of natives reported skin, kidney, hair fall, liver, and stomach issues, respectively, suspecting the crucial role of high TDS and fluoride levels in the area. This study also provides a comparison between the quality of RO and the direct supply water, along with correlation matrices for different parameters, which gives a rationale for the limitations of drinking direct supply water without any purification and RO water containing low mineral content.     

pH对铝盐絮凝剂形态分布与混凝除氟性能的影响

对比研究了AlC13和3种不同碱化度的聚合氯化铝(PACl)在不同pH与投量下除氟效果,并对不同形态铝盐除氟机理进行了初步探讨.结果表明,pH对絮凝剂水解后铝形态分布及其除氟效果有重要影响.pH 5 ～6时,Al3+和Al2、Al3等低聚态铝为AlCl3主要形态,且AlCl3更易水解生成可将溶解态氟转化为颗粒态氟的Al(OH)3,从而较PACl具有更佳除氟效果.pH ＞7时,PACl较AlCl3具有更佳除氟效果,且增大PACl碱化度可促进氟的去除,这主要是由于具有较高Al13含量的PACl更容易与电负性F-结合所致;且絮凝剂混凝除氟絮体ζ电位越高,越利于F-在絮体表面吸附.     

上海市土壤氟含量风险管控限值探讨

受工业活动影响,上海市典型工业区表层土壤氟中位值普遍高于"七五"背景值。针对工业企业场地土壤氟化物高值现象,目前仍缺乏相关的管理标准体系,且基于总量的评估分析方法已无法满足日益增长的精细化管理需求。详细梳理了国内外氟化物相关标准体系,并对上海市土壤氟限值进行了探讨。基于上海市典型工业场地特征参数计算得到的土壤氟化物筛选值高于上海市土壤"七五"背景值,与上海市工业场地调查得到的土壤氟化物高值基本持平;第一类、第二类用地的氟化物筛选建议值分别为1 980、10 000 mg/kg。与氟化物相比,水溶态氟化物是影响作物体内氟含量的重要因素,且在淋溶等作用下会对地下水安全构成威胁。考虑到水溶态氟化物的环境行为与风险,建议针对农田土壤开展水溶性氟化物含量限值研究。     

茶园土壤酸化对氟的影响及茶叶氟安全限量的探讨

在分析国内外茶园土壤酸化现状的基础上,概述了关于土壤水溶性氟与土壤pH值关系的研究进展,并通过实地调研和培养实验研究了茶园土壤酸化对土壤水溶性氟的影响.实地调研中土壤水溶性氟含量与土壤pH值无显著相关性.培养实验中,当pH＞4.00时,模拟土壤水溶性氟含量随土壤pH值的下降变化不显著;而当pH＜4.00时,土壤水溶性氟含量随着pH值的下降迅速增加,且达到极显著水平.同时描述了世界各国制订的每人每天最大摄氟量标准,对我国现行茶叶标准与国外一些国家的同类标准之间的差异做了评析.茶叶溶出实验的结果表明,我国茶叶氟安全限量需要进一步完善.     

氟化铵制备氟化钙最优条件研究

试验采用氟化铵与石灰石粉、石灰乳反应制取氟化钙,研究了反应温度、物料浓度、物料过量系数等各主要参数变化对氟化钙结晶、过滤速度、氟收率及其含量的影响,摸索出最优反应条件。     

高氟病区茶园土壤氟形态及其分布特征

采用连续化学提取法,测定了黔西北高氟病区茶园土壤样品氟含量及氟的形态.结果表明:供试土壤全氟含量为314~3558mg/kg,平均为945mg/kg,高于全国土壤全氟平均含量(453mg/kg).不同类型供试土壤中全氟含量高低顺序为:棕壤和褐土(分别为1118和1114mg/kg)>黄棕壤(908mg/kg)>黄壤(681mg/kg).供试土壤中不同形态氟含量以残余态最高,其平均含量为940mg/kg;其次为有机束缚态氟,平均含量为7.82mg/kg,处于氟污染较高水平,可能会对人体健康和生态环境产生重要影响;铁锰结合态氟也较高,平均含量3.99mg/kg;水溶态氟和可交换态氟均较低,其平均含量分别为:1.98,1.14mg/kg.由此可见,土壤中氟形态大部分均以残余态形式存在于土壤中,可被茶树叶吸收的水溶态氟和可交换态氟含量均不高.相关性分析表明:可交换态氟只与水溶态氟呈显著正相关关系(r=0.459**),而水溶态氟与铁锰结合态氟、残余态氟和全氟均呈正相关关系(r分别为0.240*, 0.226*, 0.229*), 有机束缚态氟与铁锰结合态氟、残余态氟和全氟也呈正相关关系(r分别为0.757**, 0.312**, 0.320**),水溶态氟与土壤交换性盐基含量之间也呈极显著正相关关系,而土壤氟形态与有机质的相关性不明显,仅有机束缚态氟与土壤有机质呈弱负相关.本研究可为该区域土壤氟污染防治提供科学依据,也为土壤氟的迁移转化及其对生态和环境的影响研究奠定一定的理论基础.     

Ionic composition of submicron particles (PM1.0) during the long-lasting haze period in January 2013 in Wuhan, central China

In January 2013, a long-lasting severe haze episode occurred in Northern and Central China; at its maximum, it covered a land area of approximately 1.4 million km². In Wuhan, the largest city in Central China, this event was the most severe haze episode in the 21st century. Aerosol samples of submicron particles (PM_1.0) were collected during the long-lasting haze episode at an urban site and a suburban site in Wuhan to investigate the ion characteristics of PM_1.0 in this area. The mass concentrations of PM_1.0 and its water-soluble inorganic ions (WSIIs) were almost at the same levels at two sites, which indicates that PM_1.0 pollution occurs on a regional scale in Wuhan. WSIIs (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl^-, NO₃^- and SO₄^2-) were the dominant chemical species and constituted up to 48.4% and 47.4% of PM_1.0 at WD and TH, respectively. The concentrations of PM_1.0 and WSIIs on haze days were approximately two times higher than on normal days. The ion balance calculations indicate that the particles were more acidic on haze days than on normal days. The results of the back trajectory analysis imply that the high concentrations of PM_1.0 and its water-soluble inorganic ions may be caused by stagnant weather conditions in Wuhan.     

柱状污泥基活性炭制备方法及其除污染效能研究

以城市污水厂剩余污泥为原料,用氯化锌活化法研究一种柱状污泥基活性炭(CSAC)的制备方法及其工艺条件优化,并选择粉末污泥基活性炭(PSAC)和一种商品煤质碳(MAC)作为对照,考察了CSAC对重金属离子Cu(Ⅱ)和Pb(Ⅱ)及有机污染物硝基苯的吸附去除效能.结果表明,CSAC的比表面积及微孔容积分别是306.9 m2·g-1和0.109 cm3·g-1,仅为MAC的36.7%和23.6%,但其对Cu(Ⅱ)和Pb(Ⅱ)的平衡吸附量却远远高于MAC,说明CSAC表面存在的高含量酸性官能团在吸附去除重金属过程中起到了重要的作用.由于制备原料相同及制备工艺相似,CSAC与PSAC的理化性质基本相同,两种炭的表面酸性官能团含量较高,对Cu(Ⅱ)和Pb(Ⅱ)均具有较好的吸附去除效果,优于MAC,只是CSAC的比表面积和微孔容积略低于PSAC;在对硝基苯的吸附实验中,CSAC及PSAC的吸附效率均远远低于MAC,说明在对有机物硝基苯的吸附中,活性炭的比表面积等物理性质起到了较大的作用.同时,所制备的CSAC的稳定度大于95%,易于分离回收,不会造成二次污染,适合废水中重金属离子的吸附去除.     

广州雾霾期间气溶胶水溶性离子的日变化特征及形成机制

为研究雾霾天气下SO42-、NO3-和NH4+的形成机制,2013年4月18~23日,使用6级Anderson大流量采样器采集了不同粒径段的气溶胶样品,并利用离子色谱对其中的水溶性无机离子进行了分析.结果表明,广州雾霾期间PM3和PM10中总水溶性无机离子平均浓度分别为(32.7±13.3)μg/m3和(39.4±15.7)μg/m3.SO42-、NO3-和NH4+是最主要的水溶性离子,它们在PM3和PM10中占总离子质量分数分别为76%和71%.3种离子主要集中在0.49~1.5μm的液滴模态,该模态中NH4+主要以(NH4)2SO4和NH4NO3的形式存在,而凝聚模态的NH4+则主要以(NH4)2SO4和NH4HSO4的形式存在.液滴模态的SO42-主要来自雾内或颗粒表面的液相氧化反应,NO3-主要来自夜间N2O5在颗粒表面的水解反应,NH4+主要来自NH3在颗粒上进行的非均相中和反应,而这3种离子在该模态的日变化特征则很好的反映了以上的形成机制.受太阳辐射的影响,3种离子的浓度在凝聚模态均表现为白天高于夜晚.