醋酸纤维素吸附剂的制备及其性能表征

研究开发了1种球形醋酸纤维素吸附剂,对其制备方法、形态结构及其对水中4种有机氯农药的吸附性能进行了研究.扫描电镜结果表明,所制备醋酸纤维素吸附剂的外表面是一层致密的醋酸纤维素膜,内部为网状结构;对水中狄氏剂、艾氏剂、异狄氏剂、七氯4种有机氯农药有较强的吸附能力,12h后去除率均达到85%以上;并且对正辛醇-水分配系数(lgK_ow)较大的有机物具有更快的吸附速度,对七氯、艾氏剂的去除率在0·5h后可达99%.说明该吸附剂对水中亲脂性的有机物具有较高的吸附效能.     

水源水中有机物特性及其氯化活性研究

以西南某市一个地表水为水源水的M水厂为研究对象，对其原水中有机物进行富集，有机物按照操作定义分为6个部分，分别为：亲水性有机酸、亲水性有机碱、亲水中性物质、疏水性有机酸、疏水性有机碱和疏水性物质，通过富集、确定了原水中6种有机物的组成分布，研究各种有机物的消毒副产物形成潜力以及替代剂（氯胺、二氧化氯）对卤乙酸形成的影响，提出了控制消毒副产物的主要对策，研究结果表明：1）M水厂水源水属于腐殖质含量的天然水体，受污染较小；2）原水溶解性有机物中疏水性有机酸是卤乙酸的主要前体物；3）用氯胺和二氧化氯代替传统的消毒剂作为替代消毒剂，可大大降低THMs和HAAs的生成量。     

人工地下水回灌过程中溶解性有机物的去除及变化

在实验室通过模拟土壤柱研究了人工地下水回灌过程中溶解性有机物的去除及其三卤甲烷生成势和三卤甲烷生成活性的变化.利用XAD树脂将回灌水中的溶解性有机物分为3个部分：疏水性有机酸、过渡亲水性有机酸和亲水性有机物.疏水性有机酸的三卤甲烷生成活性高于过渡亲水性有机酸和亲水性有机物.土壤含水层处理（SAT）对亲水性有机物的去除率为68.51%,对疏水性有机酸和过渡亲水性有机酸的去除率分别为58.64%和41.86%.经SAT系统处理后,溶解性有机物及各有机组分的三卤甲烷生成势减少,而三卤甲烷生成活性升高.疏水性有机酸是生成三卤甲烷的主要有机组分.亲水性有机物在SAT系统进水中的三卤甲烷生成活性较低,但由于含量高,三卤甲烷生成势也较大.而过渡亲水性有机酸由于含量和三卤甲烷生成活性较低,三卤甲烷生成势也较低.     

温度、pH值对城市垃圾中有机碳溶解及其降解特性的影响

通过实验及数值模拟的方法,研究了不同温度和pH值条件下有机碳的溶解动力学特性.结果表明,提高溶液温度有利于加速易溶解有机碳的溶解速率,但不能提高固相有机碳总的溶解量.降低溶液pH值有利于固相有机碳的溶解.实验样品在所有测试环境条件下,有机碳溶解速率为0.05~0.22m3/(kg·h);易溶解有机碳占总可溶解性有机碳百分比为30%~50%;易溶解有机碳溶解速率为14~65h-1,比难溶解有机碳溶解速率高出大约3个数量级.水溶性有机碳生物可降解性实验表明,79%以上水溶性碳难以在厌氧条件下被原生菌降解.     

九龙江口水体中有机氯农药分布特征及归宿

1999-06,对九龙江口15个站位的表层水,13个站位的间隙水进行了18种有机氯农药的测定结果表明,有机氯农药总含量在表层水中的浓度范围为51.3～2479nng/L在间隙水中的浓度范围是266～33355ng/L.对不同有机氯的含量在各站位的分布特征进行了探讨,发现Methoxychlor(甲氧滴涕),Endosulfan Sulfate(硫酸硫丹),Endrinaldehyde(乙醛异狄氏剂)以及Endosulfan II(硫丹),Dieldrin(狄氏剂),Deta-HCH和Beta-HCH 7种有机氯农药在18种有机氯农药中都占主要部分;九龙江口的六六六的含量顺序:β＞δ>α＞γ;对于滴滴涕,表层水中的含量:DDE>>DDD＞DDT;间隙水中的含量:DDE>>DDT＞DDD,二者DDE的含量都在总DDTs的50%以上,说明环境中的DDTs主要降解为DDE;九龙江口有机氯农药随着盐度梯度,在河口中呈去除趋势;且间隙水中有机氯农药比表层水中的浓度高,说明其倾向于吸附在沉积物颗粒上,其浓度差使得有机污染物可能通过再悬浮等过程从底层向上层迁移.九龙江口的有机氯农药污染与其他港湾相比,污染水平相当,部分站位水质有机氯农药(HCHs和DDTs)超过国家一类水质的标准.     

生物活性炭内吸附与生物降解协同去除有机污染物

本研究建立了一个确定BAC内2种机理去除有机物分配比例的试验方法.该方法以BAC进出水中溶解性有机碳（DOC）与可生物降解有机碳（BDOC）浓度变化作为评价参数,并利用此方法确定了臭氧投加量对2种去除机理的影响.臭氧化可以使BDOC浓度增加,臭氧投量为2～8mg/L时,BDOC增加0.12～0.54mg/L;BAC过滤使出水BDOC浓度降低为0.23～0.31mg/L.随着臭氧投量增加（2～8mg/L）,在BAC内生物降解作用去除有机物比例从46%增加到89%.     

微污染水源水中有机物的分布特征及微滤膜对其的影响作用

本试验是在微污染水源水中有机物分布调查的基础上,采用聚偏氟乙烯(PVDF)微滤膜(MF)过滤微污染地表水,考察微滤膜对天然水中有机物的影响作用.试验结果表明,黄浦江微污染水源水中的有机物分子质量主要集中在3~5 k Da和0.2 k Da附近,且疏水性有机物和亲水性有机物所占的比例相当.有机物季节性分布特征明显,冬季溶解性有机碳(DOC)的值偏高,而UV254和比紫外吸光度值(SUVA)则在夏季偏高.黄浦江原水经微滤膜过滤后,有机物构成发生明显变化,膜出水中的亲水性有机物的比例增加,而疏水性有机物的比例降低,DOC和UV254的平均去除率分别为17.73%和15.75%.黄浦江原水及经0.45μm滤膜过滤以去除悬浮物的黄浦江原水分别进行微滤膜过滤,膜比通量的对比发现,在较短时间内两者的膜比通量下降都很明显,而后膜比通量都趋于平缓,变化趋势及结果基本一致,可见,黄浦江水中造成膜通量下降的物质并不是悬浮物,而是溶解性的有机物质.     

用沉积物、稀有鮈鲫和生物模拟采样器评价水体中PAHs和OCPs的生物富集和有效性

以官厅湿地为研究对象,通过分析多环芳烃(PAHs)和有机氯农药(OCPs)在沉积物中的浓度及在30 d暴露笼养稀有鮈鲫和三油酸甘油脂-醋酸纤维素复合膜(TECAM)中的富集水平,来评价PAHs和OCPs在水体中不同介质中的富集规律,并探讨了用TECAM膜对水生生物进行生物有效性评价的可行性.结果表明,目标污染物的沉积物生物富集系数(BSAF)和沉积物TECAM膜富集系数(TSAF)在湿地各点之间均存在着较大差异,变异系数分别在10%～70%和20%～50%之间,且BSAF和TSAF与Kow均没有一致的变化规律.对于所研究的目标污染物尤其是PAHs,稀有鮈鲫的BSAF值比平衡分配模型的预测值(在1～4之间)小1个数量级左右,而TSAF值则比较接近水生生物的模型预测值.同时也发现湿地中OCPs的BSAF和TSAF相互之间存在较好的相关关系,5个实验点相关系数分别为0.80、 0.87、 0.83、 0.85和0.84(p<0.01),而PAHs的BSAF和TSAF相关关系不显著(p>0.1).由此可见,联合应用沉积物、稀有鮈鲫和TECAM膜能更可靠更准确地评价PAHs和OCPs这类有机污染物在水体中的污染状况,TECAM膜作为一种生物模拟采样器能很好地预测鱼对OCPs这类较难降解有机污染物的生物富集,是对水体中疏水性有机污染物进行生态风险评价的一个有力工具.     

黄浦江表层沉积物中有机氯农药的分布特征及风险评价

用双柱GC/ECD对黄浦江表层沉积物中的20种有机氯农药进行了分析 沉积物中总有机氯农药含量范围为2.65～19.54ng/g ,含量较高的组分有DDTs、BHCs、甲氧氯和狄氏剂等,DDTs含量高于BHCs ,含量范围分别为0.68～4.43ng/g和0.14～0.77ng/g 从上游到下游沉积物中有机氯农药含量呈升高趋势,说明工业污染及苏州河对黄浦江中下游水环境中的有机氯农药具有较大的输入贡献.有机氯农药组分分布特征研究表明,当前沉积物中的有机氯农药主要来自于早期残留或是施用农药长期风化后的土壤.相关性分析表明,总有机碳是影响沉积物中有机氯农药分布的重要因素.与其它地区相比较,黄浦江沉积物中有机氯农药含量较低.与沉积物风险评估值相比较,黄浦江中下游沉积物存在一定的生态风险.     

用沉积物、稀有鲫和生物模拟采样器评价水体中PAHs和OCPs的生物富集和有效性

以官厅湿地为研究对象,通过分析多环芳烃（PAHs）和有机氯农药（OCPs）在沉积物中的浓度及在30 d暴露笼养稀有鲫和三油酸甘油脂-醋酸纤维素复合膜（TECAM）中的富集水平,来评价PAHs和OCPs在水体中不同介质中的富集规律,并探讨了用TECAM膜对水生生物进行生物有效性评价的可行性.结果表明,目标污染物的沉积物生物富集系数（BSAF）和沉积物TECAM膜富集系数（TSAF）在湿地各点之间均存在着较大差异,变异系数分别在10%～70%和20%～50%之间,且BSAF和TSAF与K_ow均没有一致的变化规律.对于所研究的目标污染物尤其是PAHs,稀有鲫的BSAF值比平衡分配模型的预测值（在1～4之间）小1个数量级左右,而TSAF值则比较接近水生生物的模型预测值.同时也发现湿地中OCPs的BSAF和TSAF相互之间存在较好的相关关系,5个实验点相关系数分别为0.80、 0.87、 0.83、 0.85和0.84（p<0.01）,而PAHs的BSAF和TSAF相关关系不显著(p>0.1).由此可见,联合应用沉积物、稀有鲫和TECAM膜能更可靠更准确地评价PAHs和OCPs这类有机污染物在水体中的污染状况,TECAM膜作为一种生物模拟采样器能很好地预测鱼对OCPs这类较难降解有机污染物的生物富集,是对水体中疏水性有机污染物进行生态风险评价的一个有力工具.     

UV-C辐照对河水溶解有机质降解及微生物可利用性的影响

从黄浦江及其上游支流采集表层水样,进行了微生物培养、UV-C辐照和微生物再培养等处理过程,测定水样ρ(DOC)(DOC为溶解有机碳)、紫外可见吸收光谱和荧光光谱,探讨河水DOM(溶解有机质)的光化学降解和微生物可利用性特征. 结果表明:不同处理过程对DOM不同组分去除的贡献率不同,黄浦江河水经微生物培养后,ρ(DOC)和CDOM(有色溶解有机质)含量〔以a₃₃₅(335nm处的吸收系数)计〕分别下降了5%~27%和5%左右,而FDOM(荧光溶解性有机质)含量(以最大荧光强度表示)稍有增加;继续经UV-C辐照24h后,ρ(DOC)和CDOM含量分别下降了7%~36%和79%~96%,而FDOM含量下降了95%以上,说明水体中大部分CDOM和FDOM可通过UV-C辐照去除,并且去除率显著高于微生物降解. UV-C辐照不仅可以降解DOM,而且可以改变DOM的微生物可利用性,其中一部分SLDOM(半活性溶解有机质)经UV-C辐照后能够再次被微生物利用,其中4%~28%的DOC和5%~14%的CDOM可再次被微生物降解.      

巢湖溶解性有机物时空分布规律及其影响因素

为研究巢湖溶解性有机物(dissolved organic matter,DOM)的时空分布规律及其影响因素,于2013年4月至2014年4月每月在巢湖3个不同湖区17个点位采集表层水样,测定了水体溶解性有机碳(dissolved organic carbon,DOC)和溶解性有机氮(dissolved organic nitrogen,DON)浓度.结果表明,东部、中部和西部这3个湖区DON浓度具有显著差异(P0.01,n=13),这可能与西湖区入湖河流的外源输入以及DON的可利用性有关.水华期间,水体总氮总磷比、总溶解性氮磷比以及溶解性无机氮(dissolved inorganic nitrogen,DIN)与溶解性活性磷(soluble reactive phosphorus,SRP)比值迅速降低,其中西湖区DIN/SRP在2013年8月降至5±7,表明水体出现氮限制.此外,DON浓度迅速降低,西部湖区叶绿素浓度与DON显著负相关(r=-0.265,P0.05,n=91),表明在氮限制条件下,DON具有一定生物可利用性.DOC浓度不存在显著空间差异,水温是控制这3个湖区DOC浓度变化的重要因素.东部和中部湖区DOC浓度还受叶绿素和硝态氮浓度的影响.此外,巢湖DOC/DON变幅较大,由于含氮化合物更易降解,因此DON是影响碳氮比值的主导因子,是表征DOM可利用性的重要组分.     

海河与渤海湾水体中溶解态多氯联苯和有机氯农药污染状况调查

在夏季对海河与渤海湾表层水中溶解态的多氯联苯（PCBs）和有机氯农药（OCPs）的污染状况进行了调查．结果表明,海河和渤海湾表层水中PCBs、六六六和滴滴涕的含量分别为0.06～3.11 μg/L、0.05～1.07 μg/L和0.01～0.15 μg/L．海河干流流域内的工业废水排放等陆源输入可能是渤海湾中PCBs和OCPs的重要来源．研究表明该地区PCBs与水中的DOC（dissolved organic carbon）具有一定的正相关．与国内外类似水体相比,海河中PCBs和OCPs污染情况较为严重,而渤海湾则处于中等水平．     

Influence of nonionic surfactant on the solubilization and biodegradation of phenanthrene

Phenanthrene was solubilized in two different nonionic surfactants, Tween80 and Triton X-100. The bioavailability of phenanthrane to the bacteria isolated from the petroleum contaminated soils was studied based on the rotary flasks experiments. The results showed that the concentration of nonionic surfactants above the critical micelle concentration (CMC) can increase the solubility of phenanthrene in water andwere innoxious to the phenanthrene-degrading bacteria; phenanthrene solubilized in the micelles of Tween80 was bioavailable and biodegradable. The research demonstrated the potential of surfactant-enhanced bioremediation of soils contaminated by hydrophobic organic comoounds( HOCs).     

Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.     

某冶炼厂周边土壤碳组分与铜形态的相关性

研究了浙江某冶炼污染区农田土壤有机碳组分与铜(Cu)形态的相关关系.结果表明,研究区土壤Cu形态含量为铁锰氧化物结合态残渣态碳酸盐结合态有机质结合态可交换态,其中铁锰氧化物结合态Cu和残渣态Cu含量分别占全量的39.55%和39.19%.土壤p H值和碳组分对不同形态Cu含量存在一定程度的影响,其中p H值与碳酸盐结合态Cu和铁锰氧化物结合态Cu均呈显著正相关;溶解性有机碳(DOC)含量与可交换态Cu呈极显著正相关;富里酸(FA)含量与可交换态Cu呈极显著正相关,与有机结合态Cu呈显著正相关;胡敏酸(HA)含量分别与可交换态Cu和有机结合态Cu呈极显著正相关.土壤DOC、FA、HA的动态变化对这些在移动性上存在差异的Cu形态间的相互转化会带来一定程度的影响,从而改变土壤Cu的迁移能力和生物有效性.     

土壤中多环芳烃的SPMD辅助解吸行为研究

为了开发一种表征土壤中憎水性有机污染物解吸及生物有效性的新方法,建立了半透膜被动采样装置（SPMD）研究土壤中有机污染物解吸行为的方法,利用SPMD分析了多环芳烃菲、芘和苯并［a］芘在3种不同性质土壤中的辅助解吸行为.结果表明,SPMD是一种很好地表征土壤中憎水性有机污染物解吸及生物有效性的手段. SPMD辅助解吸多环芳烃的效率与土壤有机质及多环芳烃性质有关.随着土壤有机质含量的降低,土壤中菲和芘的SPMD解吸率逐渐升高,对于10 mg/kg染毒水平,当土壤有机质含量由18.68%降低到0.3%时,2种化合物的解吸率分别由56.45%和48.28%上升到接近100%;但是对于苯并［a］芘,粘土表现出明显的滞留能力,在有机质含量（0.3%）很低、粘土含量（39.05%）较高的3号土壤中,苯并［a］芘的解吸率仅有66.97%.不同多环芳烃SPMD辅助解吸率差别很大,随着土壤有机质含量的降低,以及污染物浓度的提高,菲和芘的解吸差异逐渐缩小,而苯并［a］芘与上述2种多环芳烃的差异很大,主要是由于苯并［a］芘具有高度亲脂性,并且分子较大,造成其容易滞留在粘土的微孔及有机质的致密结构中.     

The biotic ligand model: a model of the acute toxicity of metals to aquatic life

The United States Environmental Protection Agency (USEPA) has established nationally applicable water quality criteria (WQC) for metals that are designed to be protective of aquatic life. However, in some instances these criteria may be over-protective as a result of natural, site-specific differences in water quality characteristics. These differences affect metal speciation and bioavailability, fundamental considerations in assessing toxicity. Laboratory studies completed during recent years have advanced the current understanding of metal chemistry in aquatic systems, including the formation of organic and inorganic metal complexes and sorption to particulate organic matter. Parallel investigations have led to an improved understanding of the physiological basis of why metals are toxic to aquatic organisms. These studies have, in combination, led to an improved understanding of how site-specific water chemistry affects bioavailability, and how metals exert toxicity at the organism site of action, at the biotic ligand in the context of the model to be described. The biotic ligand model provides a quantitative framework for assessing metal toxicity over a range of hardness, pH and dissolved organic carbon (DOC) levels. The chemical equilibrium sub-model incorporates metal-biotic ligand interactions to compute metal accumulation at the site of action (e.g., the gill of a fish) as a function of water quality. The toxicity sub-model uses this computed accumulation level as the basis for successfully predicting observed variations in toxicity associated with changes in water quality. The results highlight the potential utility of this approach to provide an alternative means of developing site-specific permit limits and WQC. The ability of the model framework to quantitatively assess the effects of hardness, pH and DOC on toxicity, in comparison to current WQC for metals that typically vary with hardness alone, is a significant advance in understanding how site-specific conditions affect the toxicity of metals.     

Dissolved Organic Carbon in Upland Forested Watersheds Underlain by Continuous Permafrost in Central Siberia

Hydroclimatic variability and plant species ecology cause mosaics in forested watersheds in permafrost zones. Measurements of organic matter accumulation, stock of dissolved organic carbon (DOC), DOC concentrations in litter leachates, subsurface flow, stream and seasonal and annual export were made in two contrasting slopes and valleys in the northern taiga of Central Siberia. Increased organic carbon accumulation in litter was found in poor hydroclimatic conditions of the north-facing slope and bottom valleys. In contrast, DOC contents and its export to soil were almost two-fold higher in warmer well-drained sites of the south-facing slope. The overall DOC flux to mineral soil from the beginning of June to mid-September was 17 g C m⁻² in the south-facing slope sites and only 9 g C m⁻² in the north-facing slope sites. DOC export was positively correlated with precipitation stimulating leaching of mobilizable organic matter. Accordingly intra-seasonal and inter-annual variability of the DOC fluxes was tightly coupled with water input. Meanwhile DOC export in Sphagnum and feathermoss sites showed different behavior in dry and wet years. The presence of permafrost preventing deep seepage of organic solutes results in higher stream DOC fluxes compared to permafrost-free or island permafrost regions. However, thawing of seasonally frozen soil layer during the growing season led to the decreasing concentrations of DOC in the stream from June to September. For two seasons of continuous stream water sampling (June and August–September), the riverine DOC flux constituted about 14% of DOC entering mineral soil on both slopes. The ratio of hydrologic DOC loss to NPP of larch forests of the region was estimated to be 1.1%.