海河流域河流耗氧污染变化趋势及氧亏分布研究

耗氧污染是海河流域河流水污染的主要类型,耗氧污染物对河流溶氧的消耗产生的氧亏效应对水生生物产生重大影响.收集海河流域重点水功能区88个监测站点2000—2011年CODCr/CODMn、NH3-N指标,分析河流耗氧污染特征及演变趋势,并基于水质目标(2 mg·L-1)下计算出海河流域河流氧亏量.结果表明,流域河流耗氧污染总体呈现好转趋势,耗氧污染指标(NH3-N、CODCr/CODMn)逐渐降低,I~III类水质站点比例增加,劣V类水质站点数和超标倍数减少;CODMn降低幅度大于NH3-N,主要污染物由COD向NH3-N转化.海河流域重点氧亏区域主要集中于中部平原段和下游滨海段,未氧亏区域多集中于上游山区段;北三河、黑龙港运东与徒骇马颊河水系中部平原段整体处于缺氧区域,子牙河水系中部平原区缺氧现象最为严重,氧亏区域位于石家庄洨河下游、滏阳河艾辛庄下游至献县段及石津总干以南;海河流域内中部平原段河流氧亏的主要贡献仍以COD为主,但氨氮的贡献显著,其中黑龙港运东水系、徒骇马颊河水系和北三河水系,COD耗氧均值都高于5 mg·L-1,在北三河和子牙河水系,氨氮耗氧均值达到了4 mg·L-1.     

感潮河段盐度和缺氧水体时空分布规律研究

感潮河段水体的物质输运规律及其时空分布不仅受径流、潮汐动力的双重影响,还受水闸调度等人类活动的影响.针对水闸调度影响下感潮河段复杂的水动力学及其伴随的物质输运过程,提出一种新的算盘式网格结构,建立了水动力学和物质输送的三维数学模型,考察了在径流、潮汐及水闸调度综合作用下,感潮河段水流密度分层的特点,并对水体中溶解氧和盐度的时空分布规律及其影响因素进行研究.结果发现,数值模拟计算结果与观测值吻合良好,表明所建立的三维数值模型可以很好地预测感潮河段的水流运动和物质输运规律.研究表明,感潮河段的缺氧水体首先出现在盐水楔的前端,在盐-淡水分层强度、盐水停留时间及水闸调度的综合作用下,出现溶解氧浓度持续降低的趋势,并导致缺氧水体范围从河口上游向下游扩展,随水闸的放流缺氧水体被冲刷的现象.     

Rose Bengal‐sensitized photooxygenation of chlorohydroxyaromatic contaminants in water: A kinetic study

A kinetic study of the RB‐sensitized photooxygenation of a series of chlorohydroxyaromatic (ClArOH) water contaminants (phenolic and dihydroxybenzene derivatives) has been carried out. In addition, an exhaustive study on the possible interactions of RB electronically excited triplet and singlet states with ClArOH was also developed. The determination of relative rates of oxygen uptake upon sensitized irradiation, employing auxiliar selective quenchers of oxygen active species, indicate the contribution of both singlet molecular oxygen (ca. 71%) and Superoxide ion (ca. 26%) as the reactive pathways for ClArOH degradation. The substitution by chlorine atoms in position meta greatly decrease the photooxygenation rate of the phenolic derivatives. For the dihydroxybenzene series, increase in nuclear chlorination parallels a decrease in the photodegradation rate.

Outdoors sensitized solar irradiation experiments on different ClArOH mixtures leads to measurable levels of oxygen after a few minutes exposure. From the environmental point of view, and ruling out the possibility of direct‐irradiation photoreactions, sensitized photooxygenation appears as an alternative pathway for ClArOH degradation, in competence with other naturally‐occurring photoprocesses involving reactive transient species.     

枯季乌江河流“呼吸”作用及其性质探讨

发源于云贵高原上的乌江是长江流域的重要支流之一。乌江流域喀斯特地貌广泛发育，是中国南方典型的喀斯特河流。以枯水季节乌江流域水体中的实测温度、溶解氧、碱度和pH值等理化参数为依据，探讨了乌江流域河道水体的CO2分压(〖WTBX〗P〖WTBZ〗CO2)与河流“呼吸”通量的变化规律。乌江流域枯水季节河道水体〖WTBX〗P〖WTBZ〗CO2介于2913~1 530 μatm之间，平均值为9493 μatm，约为大气的3倍，各支流样点的平均值为9924 μatm，大于干流平均值9026 μatm，由此推断乌江流域干支流河道在枯季是大气CO2的“源”。受各游段流域特征以及人类活动的影响，干支流河道水体〖WTBX〗P〖WTBZ〗CO2表现出明显的空间差异。水体〖WTBX〗P〖WTBZ〗CO2与溶解氧的相关关系不显著，说明河道内有机质的异养呼吸不是喀斯特乌江流域枯季水体中溶解无机碳的主要来源，其河道水体中高〖WTBX〗P〖WTBZ〗CO2成因复杂。〖WTBX〗P〖WTBZ〗CO2的上述分布规律是流域支流汇入、地下水以及河道水体有机质氧化分解等共同作用的结果。     

Luminescence in the oxidation of isoproterenol by the superoxide anion radical in dimethyl sulfoxide

Chemiluminescence appearing during oxidation of isoproterenol using chemical system involving superoxide anion radical has been studied. Chemiluminescence and fluorescence spectra were measured. The chemiluminescence spectrum was measured with cut‐off filters and revealed bands with maximum at 440, 480, 550, 640 and 700 nm. The bands at 480, 640 and 700 nm were similar to those observed for singlet oxygen. The fluorescence spectrum exhibited maximum at 560 nm.

The inhibitory effect of several biologically important compounds known as O₂ ^?‐ HO^? and ¹O₂ scavengers on the light emission was studied.

The obtained results indicate that oxidation of isoproterenol by O₂ ^?‐ involves products in the electronically excited states. The data also seem to indicate the protective effect of isoproterenol on the deoxyribose degradation.     

三峡库区水库水质Streeter Phelps模型修正及COD变化规律的新探讨

水体复氧规律的研究对于预测和评价水中溶解氧含量, 确定有机污染水体的自净过程具有重要意义。天然水体中溶解氧的多少是评价水环境质量优劣的一项非常重要的指标, 是水质预测的一个重要任务。Streeter Phelps模型是目前进行河流水质研究常用的物理模型，具有良好的理论和实用价值，然而在某些特定水域，该模型的应用受到限制，主要原因是复氧系数的取定多在水流速度较大情况下得到的，而未考虑水面波动对复氧系数的影响，另外，在实际研究过程中发现三峡库区COD变化的规律出现异常：在离排污口相当远的水域，COD随时间变化趋势并不是指数衰减，而是在某个常值附近微小摆动，以往很多修正过的Streeter Phelps模型都无法解释这个现象。经研究表明：考虑波动效应后，对复氧系数进行修正能得到较好的模型计算结果；同时，COD变化规律不仅可以弄清楚，而且可以为进一步研究排污规律和泥沙运动提供科学依据。     

LONG-TERM CHANGES IN STREAMFLOW FOLLOWING LOGGING IN WESTERN OREGON AND ASSOCIATED FISHERIES IMPLICATIONS1

ABSTRACT: The long-term effect of logging on low summer streamflow was investigated with a data set of 36 years. Hydrologic records were analyzed for the period 1953 and 1988 from Watershed (WS) 1 (clear-cut logged and burned), WS 2 (unlogged control), and WS 3 (25 percent patch-cut logged and burned) in the H. J. Andrews Experimental Forest, western Cascade Range, Oregon. These records spanned 9–10 years before logging, and 21–25 years after logging and burning. Streamfiows in August were the lowest of any month, and were unaffected by occasional heavy rain that occurred at the beginning of summer. August streamfiows increased in WS 1 compared to WS 2 by 159 percent following logging in WS 1, but this increase lasted for only eight years following the start of logging in 1962. Water yield in August for 1970–1988 observed from WS 1 was 25 percent less than predicted from the control (WS 2, ANOVA, p=0.032). Water yield in August increased by 59 percent after 25 percent of the area of WS 3 was patch-cut logged and burned in 1963. In contrast to WS 1, however, water yields from WS 3 in August were consistently greater than predicted for 16 years following the start of logging, through to 1978. For the 10 years, 1979–1988, water yield observed in August from WS 3 was not different than predicted from the control (WS 2, ANOVA, p-0.175). The contrasting responses of WS 1 and 3 to logging are thought to be the result of differences in riparian vegetation caused by different geomorphic conditions. A relatively wide valley floor in WS 1 allowed the development of hardwoods in the riparian zone following logging, but the narrow valley of WS 3 and limited sediment deposits prevented establishment of riparian hardwoods. Low streamflows during summer have implications for salmonid survival. Reduced streamflow reduces the amount of rearing habitat, thus increasing competition. Combined with high water temperatures, reduced streamflow can lead directly to salmonid mortality by driving salmonids from riffles and glides, and trapping them in drying pools. Low streamflow also increases oxygen depletion caused by leaves from riparian red alders.     

土生拉乌尔菌TGRB3的生物学特性及其不同氧气浓度条件下的汞甲基化

从三峡库区消落带土壤中分离、纯化得到1株具有汞甲基化能力的细菌,对其形态、生理生化特征及16S rRNA基因序列进行分析后,鉴定为土生拉乌尔菌,并命名为RaouLtella terrigena TGRB3.研究发现,菌株TGRB3具有强酸碱和盐度适应能力,为中高温型菌,在pH=4～9和盐度0.2%～4.0%范围内均能正常生长,最适生长温度为25℃.在Hg~(2+)浓度为1000μg·L~(-1)时,菌株生长受到显著抑制.此外,在初始Hg~(2+)浓度为300 ng·L~(-1)的条件下探讨了该菌在不同氧气浓度(0、7%、14%和21%)下的生长情况及汞甲化能力.结果表明,该菌的生长不受氧气浓度的制约,但在有氧条件下生长更好,且在厌氧或低氧浓度条件下具有更强且稳定的汞甲基化能力.在氧气浓度为14%和21%的条件下,该菌的最大甲基汞含量分别为(0.54±0.01)和(1.62±0.08) ng·L~(-1),试验后期表现出较强的去甲基化现象,培养54 h后的甲基汞含量显著降低为(0.08±0.02)和(0.05±0.00) ng·L~(-1);而在氧气浓度为0和7%的条件下,最大甲基汞含量分别为(6.75±1.75)和(3.24±0.74) ng·L~(-1),且在试验周期内甲基汞持续产生,平均浓度分别为(3.23±1.39)和(1.66±0.71) ng·L~(-1).本试验结果可望为三峡库区消落带土壤汞生物甲基化机理的深入研究及汞污染风险评价等提供全新的试验材料.     

缺氧-好氧连续流亚硝化颗粒污泥反应器的启动及稳定运行

在室温下(17~19℃),通过接种成熟的亚硝化颗粒污泥于缺氧-好氧连续流反应器中,研究连续流亚硝化颗粒污泥的启动及稳定运行.结果表明,在启动阶段,颗粒污泥系统的亚硝态氮积累率(NAR)平均超过95%,成功启动了缺氧-好氧连续流亚硝化颗粒污泥系统.将好氧区溶解氧(DO)由(3±0.2) mg·L~(-1)提高到(4.5±0.2) mg·L~(-1),探究DO对于该连续流系统的影响.结果表明,在较高DO下,缺氧-好氧连续流亚硝化颗粒污泥系统仍能保持良好的亚硝化性能,平均NAR大于95%.另外,通过改变进水的水力停留时间(HRT),探究HRT对于该连续流系统的影响.较短的水力停留时间(8.4 h)会加快污泥颗粒在系统中的循环,使破碎的颗粒污泥不能及时重组,致使污泥颗粒沉淀性变差,造成污泥颗粒的流失.HRT增加到12.2h时,颗粒污泥系统得到了恢复,并且可以稳定运行.在运行末(166 d),氨氮去除率和NAR分别为86.7%和96.2%.     

纳米零价铜活化分子氧降解水中恩诺沙星

采用纳米零价铜(nanoscale zero-valent copper,nZVC)活化分子氧对水中恩诺沙星(enrofloxacin,ENR)的去除进行了系统研究.通过表征可以发现,纳米铜粉比表面积高于微米级铜粉,无孔隙结构,表面粗糙且容易团聚.纳米级ZVC活化分子氧的性能明显优于微米级ZVC,这主要归因于其较大的比表面积,更容易被腐蚀.通过探究活化机制可以发现,活化分子氧产生的H_2O_2和表面腐蚀产生的Cu+构成了新型类Fenton体系,持续释放的羟基自由基是造成水中ENR高效去除的主导活性物种;同时,反应过程中产生的超氧自由基能够促进Cu2+还原成Cu+,从而加速ENR的去除过程.反应条件对nZVC活化分子氧降解ENR有一定的影响,较高的nZVC投加量、较低ENR浓度、较高的反应温度以及强酸性条件均有利于ENR的去除.