沿海城市降水中总汞及汞同位素特征研究

大气汞沉降是汞从排放源进入地表系统最主要的迁移途径,利用汞同位素追踪汞在大气中的迁移转化规律及潜在来源对研究汞的生物地球化学循环具有重要意义.本研究于2012—2013年对厦门市小坪、坂头、鼓浪屿和洪文站点降水中总汞(THg)浓度和汞同位素的变化特征进行了研究.结果表明,厦门降水中THg浓度为1.0～59.4 ng·L~(-1),大气THg湿沉降量为13.1μg·m~(-2)·a~(-1).厦门冷、暖季降水中THg浓度相当,但由于暖季丰沛的降水量,导致暖季THg的湿沉降量约为冷季的2.5倍.降水样品中均表现出负的偶数汞同位素质量分馏(δ~(202)Hg,-2.2‰～-1.5‰)、正的奇数汞同位素非质量分馏(Δ~(199)Hg,0.08‰～0.22‰),以及轻微偏正的偶数汞同位素非质量分馏(Δ~(200)Hg,0.01‰～0.07‰).厦门降水中奇数汞同位素非质量分馏是大气汞液相光致还原反应的结果.偶数汞同位素非质量分馏不明显与其处于较低的纬度有关.厦门降水中δ~(202)Hg接近于厦门当地及贵州燃煤烟气中的δ~(202)Hg值,表明厦门降水中汞可能受到本地或传输过来的燃煤排放的影响.     

Size characterization of the associations between carbon nanotubes and humic acids in aqueous media by asymmetrical flow field-flow fractionation combined with multi-angle light scattering

This work focuses on the influence of humic acids (HAs) on the fate of carbon nanotubes (CNTs) in aqueous media. This influence was demonstrated by mixing CNT powder with HAs in aqueous solution in varying concentrations. The aqueous media containing HAs and CNTs were size-characterized by asymmetrical flow field-flow fractionation (AsFlFFF) coupled with multi-angle light scattering (MALS). This coupling yielded information concerning the size distribution of single- and multi-walled CNTs (SWCNTs and MWCNTs) and HAs under different physico-chemical conditions that can occur in environmental water. HAs can disperse individual CNTs in aqueous media. However, the difference in the physical structure between SWCNTs and MWCNTs leads to significant differences in the quantity of HA that can adsorb onto the nanotube surface and in the stability of the CNT/HA complex. Compared with MWCNTs, SWCNTs suspended in HAs are less affected by changing ionic strength with respect to stability and the amount suspended.     

两种分子量分级下DOM的组分特征及其生物毒性

分别采用超滤离心管和超滤杯两种方式制备不同分子量的溶解性有机物(DOM),探究不同的分子量分级方式对获得的DOM组成成分特征及其生物毒性效应的影响,同时判明各组分联合作用方式.DOM分别来源于城市污水厂出水(EfOM)及商品天然腐植酸(SWR-NOM).结果表明,两种分级方式获得的不同分子量DOM含有相同的荧光峰,腐殖...     

利用PARAFAC及SOM研究不同来源及粒径胶体的三维荧光光谱特征

利用三维荧光光谱法(3D-EEM)结合平行因子分析(PARAFAC)和自组织神经网络分析(SOM),解析了不同来源水体中不同粒径胶体的荧光特性,同时与挑峰法进行比较,以期寻找一种更好的分析天然胶体来源、粒径、荧光特性间关系的方法.基于PARAFAC模型,研究区水体中不同粒径胶体共解析出2个类腐殖质荧光峰(C1和C3)及3个类蛋白荧光峰(C2、C4和C5).其中,300 k Da~1μm分级胶体荧光强度最高,C1、C2、C3组分的荧光强度随粒径增大而增强,C4、C5组分的荧光强度随粒径增大而减弱.不同来源胶体(生活污水:进水和出水;农业污水:大盈和天恩桥;天然水体:吴淞口)的荧光强度变化大致规律为:吴淞口进水大盈天恩桥出水.SOM分析结果与PARAFAC一致,且可视化程度更高,但EEM-SOM模型存在输入变量多、兼具挑峰法缺点的问题.而PARAFAC-SOM模型不仅兼具了前两者的优点,还具有输入变量少、运行时间短、可靠性高等优点.同时,该模型还成功应用于胶体其他理化参数的分析(Parameters-SOM模型),使得前期工作结果系统性更强、更直观.因此,PARAFAC-SOM模型是相对较好的分析天然胶体来源、粒径、荧光特性间关系的方法.     

上海城市地表灰尘重金属污染粒级效应与生物有效性

以上海中心城区为例,在分析地表灰尘重金属污染粒级效应基础上,研究重金属赋存形态及其生物有效性.结果表明,地表灰尘平均中值粒径为132 μm,低于75 μm粒径级别颗粒物占有最大的体积含量.重金属污染显示出明显的粒级效应,随着粒径降低,重金属含量呈现明显的增加趋势,150 μm和75 μm是主要级别,其中<75 μm颗粒物污染物含量依次为Cr>Pb>Cd>Zn>Ni>Cu.对地表灰尘重金属赋存形态研究表明,Zn以碳酸盐态为主;Ni以残渣态为主;Pb主要为铁锰结合态存在,Cu和Cd则以有机态为主;Cr主要以残渣态存在.重金属活性形态比例依次为Zn>Pb>Ni>Cd>Cu>Cr.与国外城市相比,上海城市地表灰尘Zn、Pb和Ni生物活性比例较大,而Cu和Cd活性比例相对较低,Cr活性水平与其它城市相当,环境危害相对最小.     

Characterization of phosphorus species and modeling for its organic forms in eutrophic shallow lake sediments,North China

Variations of phosphorus （P） and its species in surface sediment of Baiyangdian Lake, a eutrophic shallow lake located in North China, were investigated through combination of field survey and numerical calculation based on cluster analysis. P fractionation was performed by a sequential extraction scheme, categorized as loosely bound P （NH4Cl-P）, reductant soluble P （BD-P）, metallic oxide bound P （NaOH-P）, calcium bound P （HCl-P） and organic P （Org-P）. P concentrations exhibited regional similarities and a total of four sub-areas were identified in which the same rank was HCl-P 〉 Org-P 〉 BD-P ,=NaOH-P 〉NH4Cl-E NH4Cl-P, BD-P and Org-P were found to contribute to P enrichment in overlying water column. Specifically, labile Org-P acted as a potential pool with a greater contribution in aerobic layer compared to anaerobic layer. A hysteresis （lag = 4 months） existed when labile Org-P concentration was negatively correlated with aerobic layer thickness. In view of magnitude of identified P contributors in sub-areas, higher potential of P release was present in Fuhe River and Tang River estuary areas. On the basis of calibration and verification, the mathematical model with parameter settings applied in this study was improved to serve as a tool for limnology management and eutrophic control.     

湖泊底泥土地利用对土壤中重金属铅、铜形态影响

采用田区试验研究了田间种植冬小麦条件下,底泥土地利用前后土壤中重金属铅、铜的形态演变及小麦各器官中铅、铜的富集。结果表明,随着底泥施用量的增加,土壤中重金属铅、铜的可交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态、残渣态均有不同程度的增加,本试验所有处理中,可交换态铅的质量分数范围为0.02~0.10 mg·kg-1,碳酸盐结合态铅的质量分数范围为0.04~0.24 mg·kg-1,铁锰氧化物结合态铅质量分数为0.41~1.88 mg·kg-1,有机物结合态铅质量分数范围为1.23~4.92 mg·kg-1,残渣态铅质量分数范围为4.82~23.66 mg·kg-1;各处理与对照相比,可交换态铜质量分数增加了40.00%~200.00%,碳酸盐结合态铜质量分数增加了36.84%~363.16%,铁锰氧化物结合态铜质量分数增加了7.17~45.15%,有机结合态铜质量分数增加了7.98%~62.61%,残渣态铜质量分数增加了0.12%~9.69%,各处理的残渣态铅、铜质量分数均较高。随着底泥用量增加,小麦根系、茎叶、籽粒中铅、铜质量分数均呈增加趋势,植株对重金属铅、铜的富集顺序为根系>茎叶>籽粒,铜的富集系数均大于铅。小麦籽粒产量、茎叶生物量及地上部生物量随着底泥施用量的增加,均出现了先增加后减少的现象,当小麦籽粒产量达到最大值时,籽粒中铅、铜质量分数未超出我国相应标准,依此确定底泥环境安全施用量为3051.29 t·hm-2。     

Characterization studies of a semi‐automated separation method for analysis of non‐ortho substituted polychlorinated biphenyl (PCB) congeners in environmental samples

Non‐ortho substituted polychlorinated biphenyl (PCB) congeners can account for the majority of the dioxin‐like toxicity in environmental samples, yet analysis for these congeners is difficult because other PCB congeners co‐elute with them in most Chromatographic methods. An automated method was developed which incorporates a porous graphitic carbon (PGC) column which is commercially available. Non‐ortho substituted congeners were successfully separated from interfering PCB congeners. Recoveries of non‐ortho substituted congeners were consistently reproducible (CV < 9%) when chicken eggs were fortified with individual congeners.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

PO43-和柠檬酸对稀土元素在小麦体内积累和分异的影响

基于营养液培养,添加外源稀土和ICP-MS分析技术,研究了无机配体PO₄^3-(Pi)及有机配体柠檬酸(Cit)对小麦器官中稀土元素积累和分异的影响.结果表明,不同Pi水平对小麦根中的稀土总含量(∑REE)影响较小,但显著降低叶中∑REE含量;而不同Cit水平对小麦根、叶中∑REE含量都有明显降低作用.对照植物(无Pi、Cit添加)中,稀土元素在小麦根中具有中稀土(MREE)富集及M-型四重效应分布特征,叶中有重稀土(HREE)富集及W-型四重效应分布特征.不同Pi处理对四重效应无明显作用,但进一步加强HREE在小麦叶片中的富集.添加柠檬酸使对照植物根和叶中的分异有逐渐减弱的趋势,在高浓度处理时(Cit≥150μmol·L^-),小麦根和叶中出现轻稀土(LREE)富集.