V2O5/AC在含SO2气氛中对气态Hg0的吸附脱除研究

利用固定床反应器研究了模拟烟气(N_2、SO_2、O_2)气氛下,气态Hg~0在V_2O_5/AC催化剂上的吸附脱除行为.考察了V_2O_5担载量、SO_2浓度和吸附温度等对V_2O_5/AC吸附脱除Hg~0的影响,并对V_2O_5/AC上吸附汞的形态进行了XPS分析表征.研究发现,V_2O_5/AC对Hg~0的吸附能力远大于载体AC.汞的吸附量与V_2O_5/AC中V_2O_5的质量分数有关,随着V_2O_5质量分数从0.5%增加到1.0%,汞的吸附量从75.9 μg·g~(-1)增加到89.6 μg·g~(-1) (无氧) 和115.9 μg·g~(-1)增加到185.5 μg·g~(-1) (有氧),远高于相同吸附条件下的AC上的汞吸附量 (9.6 μg·g~(-1)和23.3 μg·g~(-1)).SO_2对Hg~0的吸附有促进作用,主要是由于SO_2和Hg~0在V_2O_5/AC上发生了化学反应.但是当SO_2体积分数从500×10~(-6)增加到2 000×10~(-6)时,V_2O_5/AC对汞的吸附量只增加了5%.不同温度下的实验结果表明,V_2O_5/AC催化剂在150℃左右的吸附脱除Hg~0的能力最高,汞的吸附量达到98.5 μg·g~(-1) (无氧) 和187.7 μg·g~(-1) (有氧).XPS 分析结果表明,在V_2O_5/AC催化剂表面有HgO和HgSO_4生成,证实了V_2O_5和SO_2的作用.     

SO2对模拟燃煤烟气中汞形态分布影响的实验研究

采用OntarioHydro方法作为检测方法 ,在小型模拟燃煤烟气Hg形态转化实验台上研究了烟气中SO2 浓度、HCl浓度、O2 浓度变化对燃煤烟气中Hg形态分布的影响 .结果表明 :在CO2 O2 N2 的烟气体系中 ,加入SO2 后 ,Hg的转化率略有增加 ,随反应温度升高Hg的转化率逐渐降低 ,较高的O2 浓度可以促进Hg的氧化 .加入HCl后 ,随反应温度的升高Hg的转化率升高 ,SO2 的存在会降低Hg的转化率 ,HCl的浓度越大 ,转化率越大 ,较高的O2 浓度也可以促进Hg的氧化 .     

三峡水库蓄水至135 m后坝前及香溪河水域溶解无机汞分布特征研究

根据2004年8月在长江三峡水库坝前及香溪河水域对溶解无机汞浓度观测结果,分析了三峡水库蓄水至135 m(135～139m)1a后溶解无机汞的变化,初步探讨了影响溶解无机汞变化的因素,估算了蓄水对河流输送汞的影响.结果表明,三峡库区干流河段平均浓度为22.7ng·L-1,范围为未检出至82.6ng·L-1.较高浓度区主要集中在20m以浅的水体;香溪河溶解无机汞浓度与干流基本相当,平均浓度为18.0ng·L-1,浓度范围为未检出至61.4ng·L-1.蓄水后,溶解无机汞浓度显著升高,数量可观的汞将随着泥沙的沉降而滞留库区,值得关注和进一步深入研究.     

长寿湖水库垂直剖面不同形态汞的季节变化特征及其影响因素

分别于2013年9月至2014年7月,在三峡库区长寿湖水库设置5个采样点,分季节、分层次对水样和沉积物间隙水进行了采集和分析,考察了水库水体和沉积物间隙水不同形态汞浓度及垂向分布特征,并研究了沉积物中汞向上覆水的扩散通量.结果表明,长寿湖水库水体总汞浓度平均值为(14.77±12.24)ng·L-1,总甲基汞浓度平均值为(0.41±0.47)ng·L-1.夏秋季采样点溶解态甲基汞浓度在表层下4~8 m出现峰值,随之其值降低近湖底部再次跃增.颗粒态甲基汞浓度峰值出现在表层下8~20 m而非在沉积物-水体界面处,主要与上层水体颗粒物吸附甲基汞的沉降有关.长寿湖水库垂直剖面间隙水甲基汞峰值出现在表层下16 cm和28 cm,可能硫酸盐还原细菌活动扩展到更深的区域,从而导致了沉积物深处甲基化率的提高.间隙水溶解态甲基汞在秋季和夏季向上覆水体扩散通量分别为28.2 ng·(m2·d)-1和30.0 ng·(m2·d)-1,远高于冬季3.8ng·(m2·d)-1,这与夏秋两季水温较高有关.夏季、春季水体DMe Hg浓度与DO相关关系(r=-0.482**,P0.05;r=-0.339*,P0.01),秋季和冬季不具有相关性.     

三门峡水库水体中不同形态汞的分布特征

为了解三门峡水库水体中不同形态汞的分布特征,在丰水期和枯水期对三门峡水库进行采样,分别采用冷原子荧光光谱法(CVAFS)和蒸馏-乙基化衍生-气相色谱-冷原子荧光法(GC-CVAFS)测定水样中总汞、总甲基汞、溶解态总汞和溶解态甲基汞的浓度.结果表明,三门峡水库水体中总汞、溶解态汞和颗粒态汞浓度范围分别为1.65~9.65、0.80~3.16和0.70~7.81 ng·L~(-1),符合国家地表水环境质量标准(GB 3838-2002)一类水汞浓度标准限值;总甲基汞、溶解态甲基汞和颗粒态甲基汞浓度分别为0.05~0.36、0.02~0.14和ND~0.26 ng·L~(-1).三门峡水库水体总汞和甲基汞在季节和空间分布上没有呈现出明显的变化规律.总汞和甲基汞与未受污染的天然水体差别不大,水库未受到明显的汞污染.丰、枯水期沉积物中总汞浓度分别为(92.96±10.65)ng·g~(-1)和(80.06±19.14)ng·g~(-1),甲基汞浓度分别为(0.33±0.14)ng·g~(-1)和(0.50±0.19)ng·g~(-1).较低的甲基汞浓度说明在三门峡水库汞的迁移转化过程中,甲基化作用可能并非主要的过程,这可能与水体底层溶解氧浓度较高以及沉积物中有机质浓度较低有关.     

Environmental fate and behavior of silver nanoparticles in natural estuarine systems

Silver nanoparticles (AgNPs) are widely used in many consumer products, whereas their environmental behaviors in natural aquatic systems remain unknown, especially in natural brackish media. Therefore, it is urgent to investigate the environmental fate of AgNPs in natural brackish waters. Here, we investigated the stability of citrate-coated AgNPs in natural brackish water collected from 6 different sites with distinct salinities in the Xinglinwan Reservoir, located in Xiamen City, southeast China. The obtained results showed that AgNP colloids remained stable in low-salinity waters, which was mainly determined by the effects of dissolved organic matter (DOM) promoting the stability of the nanoparticles. However, the environmental fate of AgNPs in high-salinity waters was dominated by the salinity or ionic strength, especially the free ion concentrations of Cl^?, SO₄^2?, or S^2?, resulting in rapid sedimentation and dissolution. In addition, both DOM and salinity contributed to the environmental behavior of AgNPs in moderate-salinity waters, ultimately resulting in either colloidal stability or sedimentation. Overall, these results may reveal that AgNPs remain relatively stable for a long period in low-salinity natural waters, and that the stability might gradually decrease as AgNPs are transferred from freshwaters through brackish waters and eventually end up in seawater along the bay. Our findings also further indicate that the toxicity and potential risks of AgNPs may present more serious threats to the environment and organisms in natural freshwaters than in natural estuarine systems or seawater.     

天津市环境空气中细粒子的污染特征与来源

于2006年8─12月,在天津市中心城区采集细粒子(PM_2.5)并测定其中水溶性无机离子和元素的质量浓度,应用因子分析与多元线性回归技术解析PM_2.5的来源. 结果表明:ρ(PM_2.5)月均值为103.9～217.4 μg/m3,呈冬季最高、夏季最低的特征. 水溶性无机离子质量浓度占ρ(PM_2.5)的比例为24.90%～49.76%,其中ρ(SO₄2－),ρ(NO₃－),ρ(NH₄+)与ρ(Cl－)之和约占离子总质量浓度的90%. 在夏季,二次粒子质量浓度占ρ(PM_2.5)比例最大,这与SO₂向SO₄2-,NO₂向NO₃-的转化率升高有关. PM_2.5中Cl富集主要与燃煤等人为排放有关, 海盐源对Cl－的贡献不足20%. 天津PM_2.5中含量最高的元素为Si,约占元素总质量浓度的28.4%. 微量元素中以Zn和Pb的含量最高,二者主要来自燃煤和机动车排放. 源解析结果表明,二次污染、化石燃料燃烧、土壤尘和建筑粉尘是天津市环境空气中PM_2.5的主要来源,贡献率分别为53.4%,25.8%,12.3%和8.6%.      

三峡库区消落带沉积物对鱼体富集汞的影响

水体环境中的汞（Hg）容易被鱼体富集.为了研究三峡库区消落带沉积物对鱼体Hg含量的影响,采用不同Hg含量的消落带沉积物进行了为期90 d的模拟淹水实验.结果表明沉积物淹水后,水体总汞（THg）和甲基汞（MeHg）含量显著增加,鱼体肌肉中THg和MeHg含量不断增加,而内脏和头部中THg和MeHg含量前期不断增加,后期则有轻微减小的趋势.肌肉对Hg的富集量大于内脏和头部,后两者的富集量没有显著性差异.与对照组（无沉积物）相比沉积物的存在明显增加了鱼体富集Hg的量,而且当沉积物中Hg含量较高时,鱼体对Hg的富集量也显著增加.鱼体各部位THg和MeHg含量变化曲线高度相似,各部位对MeHg的富集系数（bioaccumulation factors,BCF）在1.93×10⁵~8.89×10⁵之间,对无机Hg的BCF在1.3×10³~12.8×10³之间,表明鱼体所富集的Hg形态上主要为MeHg.鱼体各部位MeHg和THg含量均为极显著相关,线性回归方程表明,在富集Hg的量中,MeHg占THg比例分别为：肌肉80.1%、内脏79.3%、头部66.7%.消落带沉积物再淹水后会发生一定程度的净甲基化现象产生MeHg,由于扩散作用使水体MeHg浓度在一段时间内升高,这导致了鱼体对Hg的富集量增加.因此对三峡库区大面积消落带可能存在的Hg污染风险不可忽视.     

唐岛湾网箱养殖区沉积物-水界面溶解无机氮的扩散通量

2004-08～2005-05分4个航次对唐岛湾网箱养殖区的10个站的沉积物间隙水和上覆水中的溶解无机氮营养盐（NH⁺₄-Ｎ、NO^-₃-Ｎ、NO^-₂-Ｎ）进行了现场调查, 并使用Fick第一定理对该海区沉积物-水界面溶解无机氮的扩散通量进行了估算.结果表明,网箱养殖区的上覆水和沉积物间隙水中溶解无机氮均以NO^-₃-Ｎ为主,分别占溶解无机氮总量的73.34%和61.45%;上覆水中溶解无机氮（DIN）和NO^-₃-Ｎ含量的季节变化趋势一致,在2004-10达到峰值,NH⁺₄-Ｎ的季节变化稍有不同;间隙水中溶解无机氮（DIN）和NO^-₃-Ｎ、NH⁺₄-Ｎ的变化趋势一致,表现为从5月份到8月份含量逐渐增加,到10月份达到最大,然后到次年2月份又减少;上覆水和间隙水中NO^-₂-Ｎ的含量随养殖进程表现为一个逐步积累的过程.NH⁺₄-Ｎ、NO^-₃-Ｎ和NO^-₂-Ｎ在沉积物-海水界面上的扩散通量分别为5.46、-5.04、8.71 μmol/（m²·d）,NO^-₂-Ｎ的扩散释放对唐岛湾网箱养殖区的水环境质量影响较大.     

用BaCl2滴定法快速测定硫酸盐的研究

用铬酸钡光度法、EDTA滴定法、间接原子吸收法、离子色谱法等方法测定SO42-检测上限都很低(12-200mg/L),且只适用于清洁水,若水样混浊则全引起较大的误差.有的地下水,SO42-浓度高达44000mg/L,用BaCl2滴定法测定SO42-:测试水样,以溴酚蓝做酸碱指示剂,加1∶50盐酸,调为pH=3.5,加入30ml异丙醇,以钍试剂做终点指示剂,滴加0.01mol/L BaCl2,砖红色为终点,根据BaCl2用量计算SO42-浓度.本方法快捷、准确、测定范围大,上限可达2000mg/L,克服了光度法测定浑浊水样引起误差大的缺点.     

广州城区秋季大气PM_(2.5)中主要水溶性无机离子分析

分别在广州市中心城区高楼顶(距地50m)和交通干线路边(距地1.2m),于2006年秋季连续一周采集了大气PM2.5样品,对比分析了SO42-、NO3-、Cl-、F-、Na+、NH4+、Ca2+、K+、Mg2+等9种水溶性无机离子含量。结果表明,楼顶相对充分混合大气中PM2.5的质量浓度范围59.5～129.5μg/m3,均值为83.7μg/m3;交通干线路边大气PM2.5的质量浓度范围为108.4～132.2μg/m3,均值为121.1μg/m3。9种离子总浓度平均达到50.9(楼顶)和44.1(路边)μg/m3,占PM2.5质量浓度的60.8%(楼顶)和36.4%(路边)。SO42-和NO3-为水溶性无机离子主要组成,其占PM2.5质量浓度的比例均是楼顶高于路边,显示二次气溶胶对楼顶充分混合大气中PM2.5有较大贡献,而路边样品中一次来源贡献相对较大。计算表明采样期间海盐对广州大气PM2.5中的水溶性组分贡献较小。NH4+当量浓度远小于SO42-和NO3-的当量浓度,中和度远1,反映PM2.5酸性较强,且楼项PM2.5粒子酸性高于路边样品。     

Effect of in-situ formed Al hydrates through long-term aging on enhanced particle destabilization by PACl coagulation

Aging of polyaluminum chloride (PACl) coagulants could significantly influence hydrolyzed Al speciation ruling coagulation performance. The goal of this study was to investigate Al species transformation through long-term aging and its impact on coagulation performance. Two kinds of commercial coagulants (PACl-1 and PACl-2) were stored for in-situ aging tests in six months to evaluate Al species variation with time and the performance of coagulation with natural turbid waters. The results showed that CaSO₄ precipitation easily occur in a commercial PACl coagulant with time as it contains SO₄^2? and Ca²⁺. It also activates the precipitation of gibbsite Al(OH)₃ in PACl with aging. Through 180 days aging, both monomeric Al (Al_a) and polymeric Al (Al_b) substantially transform into colloidal Al (Al_c) and precipitated for both PACl coagulants. At low turbidity (10 NTU), PACl-1 has a superior turbidity reduction rate than PACl-2, while PACl-2 performs a little better turbidity reduction at high turbidity (1000 NTU) regardless of aging time. With aging time, an obvious decrease in turbidity reduction for PACl-1 coagulation is observed at low turbidity of 10 NTU, while the improvement in turbidity reduction for PACl-2 coagulation by enhanced sweep flocculation can be achieved as Al_b mostly transform into Al_c after 150 days aging. It is concluded that dominant in-situ formed Al_c after a long time hydrolysis can improve PACl coagulation efficiency in turbidity reduction by enhanced sweep flocculation, especially for low turbidity water, but the increase in preformed Al_c in PACl would worsen particle destabilization after aging.     

浙江省四种类型土壤酸缓冲性能初析

用酸定量回漓和土壤BS-pH缓冲曲线定性比较浙江省四种类型土壤酸缓冲性能的强弱.结果表明,酸性淋溶土缓冲能力虽较弱,但缓冲区出现范围较宽(BS20—80％)且缓冲性能较持久.近中性水成土则大体相反.四种土壤对SO_4~(2-)的吸附容量甚大,吸附过程符合Freundlich方程表述的规律.水和1.0 mol/L KNO_3对土壤吸附态SO_4~(2-)解吸率甚低(<40％).     

厦门海洋性酸雨中有机弱酸的研究

以离子色谱法测定了厦门市海洋性降水中的甲、乙酸及某些阴、阳离子。用多元逐步回归和多对多双重筛选回归等数学方法,分析了降水中弱有机酸及其与阴阳离子的关系;讨论了其来源及对厦门酸雨的贡献。     

水稻甲基汞富集对大气气态单质汞浓度升高的响应研究

水稻具有很强的甲基汞(MeHg)富集能力,从而增加了汞污染地区居民甲基汞暴露的风险.本研究利用开顶气室熏蒸实验和土壤加汞培育实验探究水稻各组织中MeHg富集对大气中的气态单质汞(GEM)浓度升高的响应.结果表明:水稻根中甲基汞含量与土壤中甲基汞含量显著正相关(r=0.9462~0.9870,p0.05),与大气汞含量无线性关系(p0.05),表明水稻根中的MeHg主要来自土壤.水稻茎中甲基汞含量随土壤甲基汞含量的增加而线性增加(上部茎:r=0.8560,p0.05;下部茎:r=0.9178~0.9484,p0.05),与大气汞含量没有相关性(p0.05),但在气室熏蒸实验中上部茎中的甲基汞含量高于下部茎;而在土壤加汞培育实验中下部茎中的甲基汞含量高于上部茎,表明水稻茎主要受土壤汞的影响,且大气汞可能对水稻上部茎甲基汞的富集有一定的影响.水稻叶中甲基汞含量与土壤甲基汞含量显著正相关(r=0.9708,p0.01),与大气汞含量无线性关系,但在气室熏蒸实验中实验组叶中甲基汞的含量高于对照组,表明水稻叶中的甲基汞可能受土壤甲基汞和大气汞的共同影响.水稻籽粒中甲基汞的含量与土壤甲基汞含量呈显著正相关(r=0.9046~0.9865,p0.05),与大气汞含量无明显的线性关系(p0.05),表明水稻籽粒中的甲基汞主要来自土壤,但在水稻上部茎和叶中甲基汞含量受一定程度大气汞含量影响的情况下势必会对水稻籽粒甲基汞的富集产生影响,但究竟有多大程度影响或量化其贡献还需进一步实验研究.     

Exposure of aboriginal people to methylmercury due to gold mining in the Amazon, Brazil

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｃｅｔｈｅｅａｒｌｙ 1980’ｓ,ｒａｐｉｄｉｎｃｒｅａｓｅｓｉｎｇｏｌｄｍｉｎｉｎｇａｃｔｉｖｉｔｉｅｓｕｓｉｎｇｍｅｒｃｕｒｙａｍａｌｇａｍａｔｉｏｎｔｅｃｈｎｉｑｕｅｉｎｍａｎｙｄｅｖｅｌｏｐｉｎｇｃｏｕｎｔｒｉｅｓｈａｓｂｅｅｎｏｎｅｏｆｔｈｅｍａｉｎｓｏｕｒｃｅｓｏｆｍｅｒｃｕｒｙｐｏｌｌｕｔｉｏｎ ,ｐａｒｔｉｃｕｌａｒｌｙｉｎｔｈｅＡｍａｚｏｎａｎｄｏｔｈｅｒｔｒｏｐｉｃａｌｒｅｇｉｏｎｓ(Ｍａｌｍ ,1990 ;Ｒａｍｅｌ,1996;Ｉｋｉｎｇｕｒａ,1996;Ｌａｃｅｒｄａ,…     

2007年北京夏季降水分段采样酸度和化学成分分析

为掌握降水酸度和污染性化学成分随降水持续时间的变化规律,对北京2007年夏季5次典型降水过程分时段采样,分别测定了pH值、电导率,并分析了其中水溶性大气污染成分SO42-、NO3-、NH4+等随时间的变化特征.结果表明,pH加权平均值在降水初期为5.70±0.73,为非酸雨;平缓期为4.35±0.56,呈酸雨特征.pH、电导率和各离子浓度随降水时间的持续而迅速下降,10~45 min后进入平缓期,各污染离子随之下降率为50%~90%.来自北京西北方向云团的降水(8月1日)pH值较高、污染物浓度较低,SO42-、NO3-和NH4+分别为65.4、23.9和117.3μeq/L;而来自偏南云团降水(8月6日)pH值较低、污染物浓度较高,SO42-、NO3-和NH4+浓度分别为310.8、95.7和249.8μeq/L.北京夏季二次粒子浓度升高,将使降水酸化加剧.     

Characteristics of size distributions and sources of water-soluble ions in Lhasa during monsoon and non-monsoon seasons

To understand the physical and chemical characteristics, particle size distribution and sources of size-separated aerosols in Lhasa, which is located on the Tibetan Plateau (TP), six sizes of aerosol samples were collected in Lhasa in 2014. Ca²⁺, NH₄⁺, NO₃^?, SO₄^2?and Cl^? were the dominant ions. The ratio of cation equivalents (CE) to anion equivalents (AE) for each particle size segment indicated that the atmospheric aerosols in Lhasa were alkaline. SO₄^2? and NO3^? could be neutralized by Ca²⁺, but could not be neutralized by NH₄⁺, according to the [NH₄⁺]/[NO₃^??+?SO₄^2?] and [Ca²⁺]/[NO₃^??+?SO₄^2?] ratios. Mobile sources were dominant in PM_0.95–1.5, PM_1.5–3 and PM_3–7.2, while stationary sources were dominant in the other three size fractions according to the [NO₃^?]/[SO₄^2?] ratios. The particle size distribution of all water-soluble ions during monsoon and non-monsoon periods was characterized by a bimodal distribution due to the different sources and formation mechanisms, and it was revealed that different ions had different sources in different seasons and different particle size segments by combining particle size distribution with correlation analysis. Source analysis of aerosols in Lhasa was performed using the Principal component analysis (PCA) for the first time, which revealed that combustion sources, motor vehicle exhaust, photochemical reaction sources and various types of dust were the main sources of Lhasa aerosols. Furthermore, Lhasa''s air quality was also affected by long-distance transmission, expressed as pollutants from South Asiaand West Asia, which were transmitted to Lhasa according to backward trajectory analysis.     

吹扫捕集-气相色谱/冷原子荧光法联用测定地表水中甲基汞研究

建立了吹扫捕集-气相色谱/冷原子荧光联用测定地表水中甲基汞的方法,具体方法:水样乙基化后转化为易挥发的甲基乙基汞,在线吹扫捕集至Tenax管,在高纯Ar作载气时加热使Tenax捕集管中各种形态的Hg热脱附,进入GC柱分离,在700℃~900℃高温下热解还原为元素汞(Hg0),进入冷原子荧光检测器进行检测.方法检出限为0.08 pg(若水样为40 mL,检出限为0.002 ng/L),相关系数可达0.9999.对不同来源的地表水进行分析,精密度<10%,加标回收率在83.4%~105%,具有操作简单、快速、灵敏度高,满足环境监测要求.