典型岩溶区地下河中溶解态脂类生物标志物来源解析及其变化特征

利用气相色谱-质谱联用仪(GC-MS)测定了青木关地下河中溶解态类脂物的含量.研究了其在地下河中的来源、组成及迁移特征.结果表明,7~11月,各溶解态类脂物的平均含量随着青木关地下河运移距离的增加呈降低趋势,其中以溶解态饱和直链脂肪酸的下降最为显著,即由最初的5 704 ng·L~(-1)下降到1 043 ng·L~(-1),减少了约81.71%.正构烷烃能够较为详尽地指征地下河中溶解性有机质来源,而饱和直链脂肪酸、脂肪醇则对藻类和细菌等微生物有较好的指示意义.随着地下河运移距离增加,有机质输入类型呈现多样化,可能与岩溶地表不均一性有关.正构烷烃三端元图解中,水生植物的输入为地下河中溶解性有机质的主要来源,其次分别为陆地高等植物和藻类、细菌等微生物,但随着地下河运移距离的增加水生植物的相对贡献量逐渐减少.青木关地下河中正构烷烃TAR值对降雨有一定的指示意义,而饱和直链脂肪酸CPI、L/H值则指示细菌降解活动.     

土壤溶解性有机质荧光特征及其与铜的络合能力

选取4种不同类型土壤和腐熟鸡粪,透析提取溶解性有机质(DOM),通过凝胶色谱、三维荧光光谱测定并分析了DOM的相对分子质量(M_r)分布、化学结构特征及其与铜的结合能力.结果表明,鸡粪DOM相对分子质量积分面积远高于其他样品,表现出其具有较高的有机物含量,泥炭土次之.暗棕壤、褐土和黑土较低,仅为鸡粪积分面积的4.5%~5%.鸡粪在中分子量段积分面积约占总物质的34.1%,低分子量段和高分子量段分别约占41.7%和24.2%.荧光光谱分析表明,各样品均出现类蛋白荧光峰(E_x/E_m=240~270/300~350 nm),在中、高分子量段(M_r500)暗棕壤存在的荧光峰消失.泥炭土出现了较为独特的可见光区类富里酸荧光峰(E_x/E_m=325/420 nm),该荧光峰和黑土的荧光峰在中、高分子量段(M_r500)都产生了红移现象.鸡粪分别出现了和黑土类似的紫外区类富里酸荧光峰,以及和泥炭土类似的可见光区类富里酸荧光峰,以及一类独特的类蛋白荧光峰(E_x/E_m=280/350 nm),但这种类蛋白荧光峰在中分子量段(500M_r12 000)消失.分析表明泥炭土与Cu的络合常数(lg K)为4.13,其他3种土壤与Cu的络合常数较小且差别不大,集中在2.10~3.10之间.鸡粪与Cu的结合能力最大,络合常数达到6.66.     

3种生物滞留设计对城市地表径流溶解性氮的去除作用

城市地表径流溶解性氮(N)的有效控制具有挑战性.2015构建了3种不同设计的生物滞留设施:壤砂种植紫穗狼尾草(CB)、壤砂种植紫穗狼尾草设置饱和带(MB1)、壤砂种植紫穗狼尾草设置饱和带并添加10%木块(MB2).在模拟城市地表径流水文、水质变化条件下,研究3种生物滞留种植植物、设置饱和带以及添加碳源对城市地表径流溶解性N(NH_4~+-N、NO_3~--N)的去除作用.通过为期1年试验监测表明,在进水NH_4~+-N浓度平均值为(5.45±2.21)mg·L-1情况下,3种生物滞留对NH_4~+-N均具有显著的去除作用(去除率95%).基质吸附、硝化与植物吸收是生物滞留有效去除城市地表径流NH_4~+-N的主要途径.在进水NO_3~--N平均值为(5.88±2.32)mg·L-1情况下,CB、MB1和MB2出水NO_3~--N浓度的平均值分别为(4.04±2.64)、(0.84±1.18)和(0.26±0.48)mg·L-1,相应去除率分别为31.3%、85.7%和95.6%.生物滞留种植紫穗狼尾草、设置饱和带以及添加碳源均可显著降低出水NO_3~--N浓度,减少NO_3~--N淋溶输出,提高NO_3~--N去除率.植物吸收和微生物反硝化是生物滞留去除NO_3~--N的主要途径.进水NO_3~--N浓度、水量、间隔天数是影响生物滞留出水NO_3~--N浓度的主要因素.生物滞留种植紫穗狼尾草、设置饱和带并添加碳源,在水文、水质变化情况下,仍可有效去除城市地表径流溶解性N.     

长江口及邻近海域春夏季有色溶解有机物时空分布特征及主要影响因素

利用三维荧光光谱(EEMs)-平行因子(PARAFAC)分析技术对长江口及邻近海域春季(2015年3月)和夏季(2015年7月)有色溶解有机物(CDOM)的荧光组成及分布特征进行分析.共识别出2类4个荧光组分,即类腐殖质组分C1(370/495nm)、C2(330/405 nm)、C3(365/440 nm)及类蛋白质组分C4(295/345 nm).春夏季各层4个荧光组分分布模式基本一致,从长江口到邻近海域逐渐降低.春季类腐殖质组分的高值区分布在长江口内,而类蛋白组分高值区位于南槽附近区域,表层的CDOM主要来源于陆源输入和人类活动;中层荧光强度值比表层低,受陆源影响减弱;底层荧光强度值比中层略高,是由沉积物再悬浮造成的.各荧光组分在岱山县附近海域均有一个较高值,这与岛上的居民活动有关.夏季荧光组分高值区与春季相似,各层荧光组分值接近,说明夏季研究区域水体混合较均匀.春夏季腐殖化指数(HIX)在长江口较高,而生物指数(BIX)在邻近海域较高.将4个荧光组分(C1~C4)、吸收系数(a355)与盐度(S)、溶解有机碳(DOC)、总氮(TN)、总磷(TP)、叶绿素a(Chl-a)、溶解氧(DO)做冗余分析.结果表明,4个荧光组分(C1~C4)与总氮(TN)、总磷(TP)主要受陆源输入、人类活动的影响,溶解有机碳(DOC)受陆源与海源的共同影响.本文利用三维荧光光谱-平行因子分析(EEMs-PARAFAC)技术结合多元统计方法解析了CDOM组成,清晰揭示了长江口及邻近海域CDOM的来源及主要影响因子,可为河口海域生源要素海洋生物地球化学研究提供有益的补充.     

桉树叶提取液还原石墨烯电极提高微生物燃料电池产电性能的研究

将桉树叶提取液绿色还原氧化石墨烯(G-rGO)电极和微生物还原氧化石墨烯(B-rGO)电极依次作为微生物燃料电池(MFC)阳极,采用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)对所制备的电极进行表征,并采用循环伏安法(CV)、交流阻抗法(EIS)对比2种电极的电化学性能.结果发现,G-rGO阳极的内阻为243.87Ω,应用于MFC时最大功率密度和最大输出电压分别为18.77 W·m~(-3)和760 mV,对照组B-rGO电极的内阻为299.11Ω,将其应用于MFC时最大功率密度和最大输出电压分别为13.16 W·m~(-3)和635 mV,对照组未修饰阳极的内阻为375.21Ω,最大功率密度和最大输出电压分别为8.97 W·m~(-3)和480 mV.研究表明,G-rGO电极电阻更小,导电性能更优越.     

金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

磁性氮掺石墨烯活化过硫酸钾降解水中亚甲基蓝

活化过硫酸盐产生硫酸根自由基的高级氧化技术在水环境污染物治理中引起了广泛的关注和研究.本研究采用水热法制备磁性氮掺石墨烯(M-N-G)作为催化剂.利用SEM、BET、XRD和VSM等手段表征材料,系统研究了该材料活化过硫酸盐降解亚甲基蓝的效能.结果表明:M-N-G的比表面积为94.35 m2·g-1,磁性Fe3O4分布在材料表面,能有效的活化过硫酸钾降解亚甲基蓝.当催化剂的用量为200 mg·L~(-1),过硫酸钾浓度为0.4~0.5 mmol·L~(-1)时,在p H=3~6时对10 mg·L~(-1)亚甲基蓝的降解率达90%以上.体系温度在15~32℃时,降解速率常数在0.0227~0.0488 min-1,反应活化能为33.7 k J·mol-1.EPR分析及自由基漼灭实验证明了体系中有羟基自由基和硫酸根自由基产生.TOC分析结果表明:TOC去除率可达50%.M-N-G经过简单的稀硫酸和水洗后,可高效重复利用4次.该技术方法简单、高效、无二次污染,能为有机污染物废水处理提供一种新的方法选择.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus

Spatial distribution of arsenic (As) concentrations of irrigation water, soil and plant (rice) in a shallow tube-well (STW) command area (8 ha), and their relationship with Fe, Mn and P were studied. Arsenic concentrations of water in the 110 m long irrigation channel clearly decreased with distance from the STW point, the range being 68-136 μg L⁻¹. Such decreasing trend was also noticed with Fe and P concentrations, but the trend for Mn concentrations was not remarkable. Concerning soil As, the concentration showed a decreasing tendency with distance from the pump. The NH₄-oxalate extractable As contributed 36% of total As and this amount of As was associated with poorly crystalline Fe-oxides. Furthermore only 22% of total As was phosphate extractable so that most of the As was tightly retained by soil constituents and was not readily exchangeable by phosphate. Soil As (both total and extractable As) was significantly and positively correlated with rice grain As (0.296 ± 0.063 μg g⁻¹, n = 56). Next to drinking water, rice could be a potential source of As exposure of the people living in the As affected areas of Bangladesh.