水污染联防助推淮河流域综合管理

我国各大流域都面临水资源保护与水污染防治的问题,其中,淮河流域的水污染形势严峻,严重制约流域的经济社会发展。淮河流域水资源年际变化大、年内分配不均,旱涝灾害频繁。同时,流域人口密度大,经济发展水平相对落后,产业结构调整难度大,水资源供需矛盾突出,迫切需要进行流域综合治理。     

沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.     

单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

组合型生态浮床对上覆水和沉积物之间氮磷的影响

在天鹅湖水体中构建以水生植物和陆生喜水植物为实验植物,浮法控制器、水循环增氧系统和造浪-输送系统为辅助设备的组合型生态浮床.组合型生态浮床运行期间改变了水体的理化环境,影响了上覆水-沉积物中氮磷形态的迁移转化,跟踪监测在组合型生态浮床影响下上覆水和沉积物TN、NH4+-N和TP含量的浓度变化规律,探讨了在组合型生态浮床作用下,DO、Eh、pH对上覆水和沉积物中营养盐的影响,以及上覆水和沉积物中氮磷之间以及和各环境因子之间的相互关系.结果表明,实验期间上覆水中TN、NH4+-N和TP的去除率分别达到61.92%、63.09%和80.0%.沉积物中TN和NH4+-N的去除率分别达到23.79%和37.04%,沉积物中TP含量上升了43.71%.组合型生态浮床对上覆水环境因子如DO、Eh、pH等产生不同程度的影响,处理区上覆水中DO和Eh均高于对照区,DO由原来的8.7～8.9 mg·L-1上升到9.3～10.4 mg·L-1,Eh由原来的163～178 mV上升到191～198 mV,通过提高上覆水中DO和Eh有效抑制沉积物磷的释放并促进沉积物对上覆水中磷的吸附.pH的波动性较小,维持在7.51～8.32之间,并未促进沉积物磷释放.上覆水中TN、TP和NH4+-N以及与沉积物中的TN、NH4+-N之间呈极显著正相关,与沉积物中的TP极显著负相关;pH与上覆水和沉积物中的TN、TP和NH4+-N都无相关性;上覆水中的DO与Eh显著正相关,与沉积物中的TP显著负相关.     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

以废气为热源生产二水氯化钙的新工艺

针对在氯化法生产钛白粉的过程中产生的大量高热值废气和氯化钙废水,提出以废气为热源生产二水氯化钙的新工艺。以焚烧的方式处理氯化尾气,将产生的热量用于浓缩蒸发氯化钙废水,生产工业级二水氯化钙产品,达到以废治废的目的。不仅处理了工业废气和废水,在节约能源的同时创造了一定的经济效益。     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms：An experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter （DOM） form complexes with inorganic divalent mercury （Hg^2＋） affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg^2＋ （the prevailing mercury species in the water column of these lakes） by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg^2＋ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with^197Hg^2＋. The bioavailability of Hg^2＋ was affected by the concentration and character of DOM. The entrance of Hg^2＋ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg^2＋ by Cryptomonas, up to 27% of the Hg^2＋ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg^2＋ in the dissolved phase, resulting in the lowest Hg^2＋ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg^2＋ amended. The dietary incorporation of Hg^2＋ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg^2＋ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg^2＋ by algae through competitive binding, while the incorporation of Hg^2＋ into the zooplankton was dominated by trophic or dietary transfer.     

化学铁盐辅助除磷对生物除磷的影响研究

化学辅助除磷有助于污水厂实现磷达标,但其对生物系统存在潜在的影响。针对除磷药剂对生物除磷过程的影响展开研究,选用硫酸亚铁进行化学辅助除磷。药剂形成的化学污泥干扰生物除磷过程且成分复杂,故以磷酸铁、氢氧化铁模拟化学污泥,由钾离子、K/P摩尔比计算出同步除磷中的生物除磷,来探讨化学污泥对聚磷菌释磷/吸磷过程的影响。结果表明,连续投加硫酸亚铁使聚磷菌的释磷量、吸磷量降低;系统中磷酸铁含量0.075 mmol/L时聚磷菌的释磷和吸磷能力提高了约25%,磷酸铁含量0.15 mmol/L时对聚磷菌吸磷有抑制作用;氢氧化铁对聚磷菌释磷、好氧初期吸磷均有抑制作用。生物污泥与化学污泥存在交互作用。     

ABR反应器中COD/SO_4~(2-)值和硫酸盐负荷对SO_4~(2-)去除影响

利用厌氧折流板反应器,分别考察了反应器启动,及不同COD/SO42-比值和硫酸盐负荷对模拟废水中SO42-去除的影响。实验在(32±0.1)℃,pH为6.0⁶.5的条件下连续运行。结果表明:ABR经过约90 d的启动驯化阶段后,进水硫酸盐及COD浓度分别为1 500 mg/L和3 000 mg/L,水力停留时间为12 h条件下,硫酸盐去除率达到了92%。固定COD/SO42-比值为2.5时,随着进水SO42-浓度的增加(1 5006.5的条件下连续运行。结果表明:ABR经过约90 d的启动驯化阶段后,进水硫酸盐及COD浓度分别为1 500 mg/L和3 000 mg/L,水力停留时间为12 h条件下,硫酸盐去除率达到了92%。固定COD/SO42-比值为2.5时,随着进水SO42-浓度的增加(1 500³ 500 mg/L),SO42-去除率逐渐下降,最低为60%,相反SO42-去除速率随着硫酸盐浓度的增加而增加,最大为7.98 kg(/m3.d);维持恒定的硫酸盐浓度(1 500 mg/L),逐渐缩短水力停留时间以提高反应器中硫酸盐负荷,SO42-去除率呈现先上升后下降的复杂变化趋势,当水力停留时间为6 h时,SO42-去除率达到最大;随着COD/SO42-比值的提高,硫酸盐去除能力增强,且反应体系对硫酸盐负荷的耐受能力也逐渐增强。