Investigation on Fe, Mn, Zn, Cu, Pb and Cd fractions in the natural surface coating samples and surficial sediments in the Songhua River, China

Natural surface coating samples （NSCSs） from the surface of shingles and surficial sediments （SSs） in the Songhua River, China were employed to investigate the relationship between NSCSs and SSs in fractions of heavy metals （Fe, Mn, Zn, Cu, Pb, and Cd） using the modified sequential extraction procedure （MSEP）. The results show that the differences between NSCSs and SSs in Fe fi＇actions were insignificant and Fe was dominantly present as residual phase （76.22% for NSCSs and 80.88% for SSs） and Fe-oxides phase （20.33% for NSCSs and 16.15% for SSs）. Significant variation of Mn distribution patterns between NSCSs and SSs was observed with Mn in NSCSs mainly present in Mn-oxides phase （48.27%） and that in SSs present as residual phase （45.44%）. Zn, Cu, Pb and Cd were found dominantly in residual fractions （〉48%）, and next in solid oxides/hydroxides for Zn, Pb and Cd and in easily oxidizable solids/compounds form for Cu, respectively. The heavy metal distribution patterns implied that Fe/Mn oxides both in NSCSs and SSs were more important sinks for binding and adsorption of Zn, Pb and Cd than organic matter （OM）, and inversely, higher affinity of Cu to OM than Fe/Mn oxides in NSCSs and SSs was obtained. Meanwhile, it was found that the distributions of heavy metals in NSCSs and SSs were similar to each other and the pseudo-total concentrations of Zn, Cu, Pb and Cd in NSCSs were greater than those in SSs, highlighting the more importance for NSCSs than SSs in controlling behaviours of heavy metals in aquatic environments.     

Scavenging of Cd through Fe/Mn oxides within natural surface coatings

The dynamics of Cd scavenging from solutions by Fe/Mn oxides in natural surface coatings （NSCs） was investigated under laboratory conditions. Selective extraction methods were employed to estimate the contributions of Fe/Mn oxides, where hydroxylamine hydrochloride （0.01 mol/L NH2OH-HCl ＋ 0.01 mol/L HNO3）, sodium dithionite （0.4 mol/L Na2S2O4） and nitric acid （10% HNO3） were used as extraction reagents. The Cd scavenging was accomplished with developing periods of the NSCs （totally 21 data sets）. The resulting process dynamics fitted well to the Elovich equation, demonstrating that the amount of Cd scavenged was proportional to the increments of Fe/Mn oxides that were accumulated in the NSCs. The amount of Cd bound to Fe oxides （MCdFe） and Mn oxides （MCdMn） could be quantified by solving two equations based on the properties of two extraction reagents. The amount of Cd scavenged by Fe/Mn oxides could also be estimated using MCdFe and MCdMn divided by the total amounts of Fe and Mn oxides in the NSCs, respectively. The results indicated that the Cd scavenging by Fe/Mn oxides was dominated by Fe oxides, with less roles attributed to Mn oxides. The estimated levels of Cd scavenging through Fe and Mn oxides agreed well with those predicted through additive-adsorption and linear-regression models.     

Adsorption of Pb, Cd to Fe, Mn oxides in natural freshwater surface coatings developed in different seasons

Metal oxides( Fe, Mn oxides) in natural surface coatings(biofilms and associated minerals) are believed to play a significant role n the fate and transport of trace metal in aquatic environments. Seasonal variation of Fe, Mn oxides and organic materials in surface oatings, which were developed periodically on glass slides in Nanhu Lake, Jilin Province, China over the time frame of three seasons,was investigated in order to understand the influence of metal oxides on Pb and Cd adsorption to heterogeneous surface coating materials(biofilm). Pb and Cd adsorption was measured under controlled laboratory conditions( mineral salts solution with defined speciation, ionic trength 0.05 mol/L, 25~C and pH 6.0). The classical Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb nd Cd adsorption to the surface coatings. In general, components in the surface coatings varied greatly with seasons altering and btained higher concentrations in summer while the content of iron oxides always exceeded that of manganese oxides. Correlation nalyses between the maximum adsorption of Pb and Cd and components in the surface coatings developed periodically indicated that Pb hase association with Mn oxides and Cd phase association with Fe oxides as well as Mn oxides were statistically significant. Effect of Mn xides on Cd adsorption was confirmed in view of its higher content in the surface coatings. The importance of ferromanganese oxides for b and Cd adsorption to the natural surface coatings developed in different seasons was evidenced.     

锰氧化物与环境中有机物的作用及其在环境修复中的应用

锰氧化物在陆地和海洋环境中含量丰富.作为天然强氧化剂之一,广泛地参与自然界中有机和无机化合物的氧化还原反应,锰氧化物通过吸附、氧化偶合或氧化分解等方式与多种有机物,如酚及取代酚、芳香胺、腐殖酸、氨基酸.甚至多环芳烃、多氯联苯、内分泌干扰物等相互作用,本文对锰氧化物与多种有机物的反应机理、影响锰氧化物对有机物吸附性能和反应活性的因素进行了综述.同时介绍了天然矿物锰氧化物、化学合成锰氧化物及生物氧化锰的特点及其在环境修复中的应用前景.     

Comparison of Pb and Cd adsorption to the surface coatings and surficial sediments collected in Xianghai Wetland

Surface coatings and surficial sediments were obtained in four natural waters in Xianghai Wetland in China to study the role of surface coatings and surficial sediments in controlling the transporting and cycling of heavy metals in aquatic environments. Pb and Cd adsorption to the surface coatings and surficial sediments were measured under controlled laboratory conditions(mineral salts solution with defined speciation, ionic strength 0.0.5 mol/L, 25℃ and pH 6.0 for surface coatings: and 0.00.5 mol/L CaCl2 solution, 25℃ and pH 6.0 for surficial sediments). The Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb and Cd adsorption to the surface coatings and surficial sediments, and the component analyses of surface coatings and surficial sediments were also carried out.Correlation analyses between the maximum adsorption of Pb and Cd (Гmax) and the components in the surface coatings and surficial sediments suggested that there was a statistically significant trend for Pb and Cd adsorption(Гmax) to the surface coatings to increase with increasing in contents of Fe and Mn oxides in the surface coatings and surficial sediments. And the metal adsorption abilities of surface coatings were much stronger than those of surficial sediments, highlighting that in the same water, i.e. at the same pH and initial metal concentrations, the metals(such as lead and cadmium) in supernatant were feasible to be adsorbed by surface coatings than surficial sediments. The more importance of surface coatings than surficial sediments for adsorbing and cycling of heavy metals in aquatic environments was evidenced.     

自然水体生物膜上铁、锰氧化物生长速率的研究

通过对南湖水体培养的生物膜上铁、锰氧化物生长速率的研究发现，生物膜上铁、锰氧化物的生长过程均属于一级动力学反应，可以用双常数速率方程、Elovich方程、抛物线扩散方程及指数函数方程进行描述，生物膜上铁氧化物的生长速率远远大于锰氧化物的生长速率，锰氧化物的生长速率随水深的增加而降低，并呈显著的线性关系。     

杭州市浅层地下水有机污染及其风险初步评价

针对杭州典型城市功能区的代表性浅层地下水样品进行了7种卤代烃、7种苯系物、16种多环芳烃和14种有机氯农药共44种有机污染物的定量分析,研究了浅层地下水中有机污染物的分布特征,并参照检出限和饮用水标准值,采用污染指数法和环境影响度评价方法,对浅层地下水的有机污染及其风险进行了初步评价,同时探讨了其来源。结果表明:杭州市浅层地下水中除四氯化碳外,其他卤代烃包括:1,1二氯乙烯、三氯甲烷、三氯乙烷、三氯乙烯、四氯乙烯和三溴甲烷都有检出;普遍检出多环芳烃是亚二苊氢、蒽、萘、二苊氢、菲、苯并(a)蒽、苯并(b)荧蒽和芘;有机氯农药是p,p'-DDT,其次为α-六六六、γ-六六六、δ-六六六、七氯环氧、p,p'-DDE和p,p'-DDD。杭州市浅层地下水普遍受到了卤代烃、多环芳烃和有机氯农药的轻度污染,七氯环氧和P,P'-DDT甚至达到中度污染水平。农业区、工业区和垃圾场的浅层地下水有机污染,特别是七氯环氧和三氯乙烷,已显示出明显的潜在危害作用,具有一定的健康风险。根据地球化学参数和浅层地下水环境背景推测有机污染物主要来源于化肥农药的施用、各种类型的工矿企业"三废"的排放和垃圾填埋场渗滤液。     

含铁、锰水源水深度处理工艺的运行实验研究

对铁、锰含量较高又存在有机微污染的原水进行深度处理的生产规模的净水厂（规模10m^3/h），进行了运行效能的试验研究。该水厂由射流曝气→砂滤罐→臭氧接触氧化罐→生物活性炭滤罐→木鱼石滤罐→紫外线照射清水箱等处理单元组成。通过曝气充氧－砂滤预处理，去除溶解性的二价铁60％以上,关剩余臭氧的量为0.4mg/L（相应的臭氧投量为：4mg/L)的条件下，经臭氧接触氧化和生物活性炭过滤，在HRT20min时，可去除铁锰高达100％，CODMn的去除率达90%左右。     

丹江口水库表层沉积物有机/无机磷形态特征

采用连续分级提取法研究了丹江口水库表层沉积物中有机磷和无机磷的形态及其赋存特征,同时结合间隙水体中溶解性总磷(DTP)的空间分布特征,讨论了各形态磷的生物可利用性及其释放风险.结果表明,丹江口水库沉积物中各形态磷均在入库河流处高于库区.各采样点沉积物总磷在203.08~1625.61mg/kg之间,平均值为642.51mg/kg,其中以无机磷为主,占总磷的52.9%.无机磷形态中生物可利用性差的Ca-P_i占优势,平均值为196.46mg/kg,占无机磷的57.8%;沉积物有机磷形态中活性最差的NA-P_o占绝对的优势,NA-P_o平均值为180.83mg/kg,占有机磷(OP)的59.7%. WA-P_i、PA-P_i、Fe/Al-P_i、WA-P_o、PA-P_o均与间隙水体DTP呈显著正相关(P < 0.05), Ca-P_i、MA-P_o、NA-Po与间隙水DTP相关性较差.入库河流沉积物生物可利用性磷含量及释放通量均较库区高,具有较高的释磷风险.     

佳木斯市水源地源水铁、锰含量超标的原因分析

根据佳木斯市的地质状况及近十年水源地铁、锰的监测数据,分析了佳木斯市各饮用水源地源水铁锰含量超标原因.     

Effects of nature organic matters and hydrated metal oxides on the anaerobic degradation of lindane,p,p''''-DDT and HCB in sediments

IntroductionLindane ,p,p’ DDTandHCBaresemivolatileandlipophilic ,andtheyfallintotheclassofcompoundsdescribedaspersistentorganicpollutants.Moreover,thesecompoundshavebeenidentifiedaspotentendocrinedisrupters(Smith ,2 0 0 2 ;Willett,1 998;Robert,2 0 0 1 ) .Ithasbeenreportedchlorinatedorganiccompoundscanbedecomposedveryslowlyinsedimentsthroughvariousreactions(Niesl,1 990 ) .Factorsinfluencingthebiodegradationofcompoundsarevarious.Amongthem ,itwasreportedthattheeffectsofnaturalorganicmatters…     

有机碳与水合金属氧化物对反硝化条件下河流沉积层中苯胺降解的影响

采集渭河沉积物及西安某自备井的地下水,沉积物采用逐级分离法处理后,进行厌氧微宇宙实验,研究反硝化条件下河流沉积层中苯胺降解及有机碳与水合金属氧化物的影响.结果表明,硝酸盐为50、300或400mg·L-1,沉积物中的原有或外加的有机碳都对苯胺降解具有抑制作用;去碳沉积物、去碳去金属沉积物实验中,硝酸盐为50mg·L-1时,外加有机碳具有抑制作用,当硝酸盐为300或400 mg·L-1时则有促进作用.去碳沉积物与去碳去金属沉积物的实验发现,无论是否有外加有机碳,水合金属氧化物都对河床沉积层中反硝化条件下苯胺降解具有促进作用.机理分析表明,反硝化条件下,河流沉积层中的微生物以生长代谢的方式利用苯胺,使其降解.苯胺降解经过脱氨基过程.     

三价铁促进生物氧化锰稳定土壤砷的效果和机制

通过室内模拟实验,研究了三价铁对生物氧化锰（BMO）稳定化砷污染土壤的促进效果与作用机制.实验结果表明：三价铁的添加提高了BMO对土壤中砷的稳定化效率,当三价铁以质量分数百分比（以Fe计）为0.5%、1%、2%和4%添加时,砷的稳定化效率由单独BMO处理的63.02%增加至86.04%、93.86%、96.56%和97.98%;由连续提取实验结果可知,添加三价铁能够促进土壤中砷的结合形态由可交换态、专属吸附态向无定型铁锰结合态和结晶型铁锰结合态转变,增强土壤中砷的稳定化作用;风险分析进一步表明添加三价铁后砷的环境风险由中风险转变为低风险;矿物晶体结构分析表明,添加三价铁后土壤中出现水铁矿、纤铁矿等次生铁氧化物,这些铁氧化物对土壤中砷有良好的吸附固定能力.总体而言,三价铁的存在能够提高BMO对砷污染土壤的稳定化效率,但三价铁的添加量不宜过高,否则会引起土壤酸化问题.     

南亚热带地区水库夏季铁、锰垂直分布特征

铁(Fe)和锰(Mn)均为氧化还原敏感性元素,是水质评价的重要指标之一.为了解南亚热带地区供水水库夏季Fe、Mn的垂直分布特征,于2016年7月调查了粤东地区9座水库敞水区湖沼学变量和Fe、Mn浓度的垂直分布特征.在有明显温度分层的深水水库中Fe、Mn存在显著的梯度分布,表层水体中总Fe(TFe)、总Mn(TMn)以及溶解性Fe、Mn(DFe、DMn)的浓度显著(TFe,F=6.708,P=0.032;TMn,F=9.720,P=0.014;DFe,F=8.129,P=0.029;DMn,F=11.125,P=0.016)低于底层.5座深水水库底层水体中TFe、TMn平均浓度分别为0.399 mg·L~(-1)和0.422 mg·L~(-1),其中溶解态离子占70%以上,而在没有明显温度分层的浅水水库中,表层水体TFe、TMn以及DFe、DMn浓度略低于底层但无显著性差异(TFe,F=0.135,P=0.726;TMn,F=0,P=1;DFe,F=0.006,P=0.943;DMn,F=0.007,P=0.936),4座浅水水库底层水体中TFe、TMn平均浓度分别为0.110 mg·L~(-1)和0.089 mg·L~(-1),且主要以非溶解态存在.水体中TFe和DFe浓度与溶解氧(DO)浓度、p H值和深度呈显著相关关系(P0.05),与总磷(TP)、总氮(TN)浓度没有显著相关性.水体热分层及高的水体稳定性导致DO和p H值呈现明显的梯度分布,是导致深水水库Fe、Mn在水层间形成梯度分布的关键原因.深水水库底层水体低DO浓度和酸性条件有利于沉积物中Fe、Mn的释放,是导致Fe、Mn以溶解态存在的主要原因.同时,以红壤为主的土壤类型可能是该地区水体中Fe、Mn普遍较高的重要原因.以上结果表明,南亚热带地区夏季分层稳定的深水水库底层水体普遍存在Fe、Mn较高的现象,以深层取水的供水方式易出现Fe、Mn浓度超标,湖上层取水则可避免该问题.     

海河及邻近海域表层沉积物重金属污染及其分布特征

对海河及邻近海域沉积物重金属污染程度进行调查,结果显示海河沉积物已遭受重金属污染,其重金属含量高于渤海湾,而且峰值最高的区域出现在工业发达、人口密集的天津市区和塘沽区。将海河及邻近海域表层沉积物不同颗粒组分的复合体进行分离,并进行了重金属含量的测定。结果进一步证明,重金属含量随沉积物复合体颗粒尺寸增大而减小。同时表明,渤海湾表层沉积物复合体比海河的颗粒大,砂质含量比海河高。渤海湾细小颗粒(<20μm)复合体含量(62.42%)低于海河(70.24%),而渤海湾粗砂(>200μm)组分(31.17%)比海河(17.83%)高得多。海河各粒级复合体上Cu、Pb、Cd的含量明显高于渤海湾中各粒级相应的重金属含量,平均是渤海湾的2倍左右,Cr在海河与渤海湾各粒级含量相对来说比较接近。     

程序升温条件下铁及其氧化物在CO存在时对N_2O的还原机理

应用热综合分析仪 (TG FTIR)研究了在还原性气氛下Fe及其氧化物对N2 O的催化还原作用 .研究发现铁氧化物对氮氧化物的催化还原能力相当弱 ,而Fe可以高效地降低N2 O分解的初始温度和提高N2 O向N2 的转化率 .在Fe和CO的作用下 ,N2 O的初始分解温度为 92 0K和 10 0 0K .在 112 3K时 ,N2 O的转化率达到 95 %和 80 % .TG/DSC曲线表明了在Fe与N2 O反应过程中CO的作用表现为通过与N2 O在反应表面的竞争吸附使铁氧化物还原为金属铁 ,X射线衍射证明Fe与N2 O反应后的氧化物为Fe2 O3 ;扫描电镜对反应后Fe表面物理形态的研究发现 ,在CO作用下 ,Fe的表面呈松散结构 ,可以保证Fe对氮氧化物反应的连续进行     

程序升温条件下铁及其氧化物在CO存在时对N2O的还原机理

应用热综合分析仪（TG－FTIR）研究了在还原性气氛下Fe及其氧化物对N2O的催化还原 作用。研究发现铁氧化物对氮氧化物的催化还原能力相当弱，而Fe可以高效地降低N2O分解的初始温度和提高N2O向N2的转化率。在Fe和CO的作用下，N2O的初始分解温度为920K和1000K。在1123K时，N2O的转化率达到95％和805。TG／DSC曲线表明了在Fe与N2O反应过程中CO的作用表现为通过与N2O在反应表面的竞争吸附使铁氧化物还原为金属铁，X射线衍射证明Fe与N2O反应后的氧化物为Fe2O3；扫描电镜对反应后Fe表面物理形态的研究发展，在CO作用下，Fe的表面呈松散结构，可以保证Fe对氮氧化物反应的连续进行。     

长江南京段水、悬浮物及沉积物中多氯有毒有机污染物

对长江南京段水、悬浮物及沉积物中多氯有毒有机污染物进行了分析测定,由色谱/质谱测得的结果表明,水和沉积物中多氯有机污染物的浓度较低,低于欧洲主要河流中的含量水平.悬浮物中这类污染物总含量较高,为56.45～62.35μg/kg,而水中总含量仅为14.61～15.83ng/L.由于长江中污染物被充分稀释与混匀,各采样点的水和悬浮物中该类污染物的浓度变化不大,两相间具有较好的相关性.但各采样点的沉积物中多氯有机污染物含量差异甚大,表明悬浮物的沉积极不均一.沉积物中主要污染物是六氯苯（HCB）和它的代谢产物五氯苯（PeCB）以及滴滴涕（DDT）的代谢产物,其他多氯有机污染物含量很低.     

Effects of nature organic matters and hydrated metal oxides on the anaerobic degradation of lindane, p, p '-DDT and HCB in sediments

Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ-666,p, p‘-DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ-666, p, p‘ -DDT and HCB followed pseudo-first-order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ-666, p, p ‘-DDT and HCB were 0.020 d^-1, 0.009 d^-1 and 0.035 month^-1 respectively for the sediments without additional carbon resources. However, with addition ofcarbon resources, the anaerobic degradation rates of γ-666, p, p‘-DDT and HCB were 0.071 d^1, 0.054 d^-1 and 0.088 month^-1 in the original sediments respectively. After removing NOM, the rates were decreased to 0.047 d^-, 0.037 d^-1 and 0.066 month^-1 ; in thesediments removed NOM and HMO, the rates were increased to 0.067 d^-1 , 0.059 d^-1 and 0.086 month^-1 . These results indicated that NOMin the sediments accelerated the anaerobic degradation of γ-666, p, p‘-DDT and HCB ; the HMO inhibited the anaerobic degradation of γ-666,p, p ‘-DDT and HCB.     

河流底泥中溶解性有机物的释放途径及影响因素研究

以沈阳市新开河底泥为研究对象,考察了河流底泥中溶解性有机物（DOM）的释放途径,并分析了时间、温度、pH值、底泥粒径、盐度和上覆水体中溶解性有机碳（DOC）浓度对河流底泥DOM释放的影响.此外,还研究了底泥释放对上覆水体中DOM的光谱学特性的影响.结果表明,对底泥DOM释放影响程度最高的是间隙水的混合作用,其次是底泥表层静态释放,而悬浮颗粒释放对底泥DOM释放的影响程度较小.底泥DOM的释放量随温度,pH值,底泥粒径,盐度的增大而增大.上覆水体DOC浓度较高时,DOM由上覆水体向底泥迁移.扰动作用能够影响底泥DOM的迁移.类富里酸荧光物质和类芳香族蛋白质荧光物质是底泥DOM中的主要荧光物质.河流底泥DOM向上覆水体释放的主要是激发波长分别为280~300nm和320~380nm的荧光物质.并且,扰动作用促进了荧光物质由底泥向上覆水体的释放.