薄膜扩散梯度技术在重金属生物有效态监测中的应用

重金属生物有效性是评估重金属元素迁移性、生物可利用性和生态影响的关键参数。薄膜扩散梯度技术(DGT)是一种原位被动采样技术,因其具有原位富集性、形态选择性,可提供被监测物质在监测时间段内的平均浓度等优点,可作为生物对重金属摄取的模拟替代物对环境介质中重金属的生物可利用度进行预测,已被广泛应用于环境介质中重金属生物有效性的测定。研究主要介绍了DGT技术的原理、组成和特点,评述了其近年来在水体、土壤、沉积物中重金属生物有效态应用方面的新进展,提出了DGT技术未来要提高抗生物污染能力及寻找可与DGT技术联用的相关技术的观点。     

Modeling of a sequencing batch reactor treating municipal wastewater using multi-layer perceptron and radial basis function artificial neural networks

A sequencing batch reactor was modeled using multi-layer perceptron and radial basis function artificial neural networks (MLPANN and RBFANN). Then, the effects of influent concentration (IC), filling time (FT), reaction time (RT), aeration intensity (AI), SRT and MLVSS concentration were examined on the effluent concentrations of TSS, TP, COD and NH₄⁺-N. The results showed that the optimal removal efficiencies would be obtained at FT of 1 h, RT of 6 h, aeration intensity of 0.88 m³/min and SRT of 30 days. In addition, COD and TSS removal efficiencies decreased and TP and NH₄⁺-N removal efficiencies did not change significantly with increases of influent concentration. The TSS, TP, COD and NH₄⁺-N removal efficiencies were 86%, 79%, 94% and 93%, respectively. The training procedures of all contaminants were highly collaborated for both RBFANN and MLPANN models. The results of training and testing data sets showed an almost perfect match between the experimental and the simulated effluent of TSS, TP, COD and NH₄⁺-N. The results indicated that with low experimental values of input data to train ANNs the MLPANN models compared to RBFANN models are more precise due to their higher coefficient of determination (R²) and lower root mean squared errors (RMSE) values.     

Fecal source tracking by antibiotic resistance analysis on a watershed exhibiting low resistance

The ongoing development of microbial source tracking has made it possible to identify contamination sources with varying accuracy, depending on the method used. The purpose of this study was to test the efficiency of the antibiotic resistance analysis (ARA) method under low resistance by tracking the fecal sources at Turkey Creek, Oklahoma exhibiting this condition. The resistance patterns of 772 water-isolates, tested with nine antibiotics, were analyzed by discriminant analysis (DA) utilizing a five-source library containing 2250 isolates. The library passed various representativeness tests; however, two of the pulled-sample tests suggested insufficient sampling. The resubstitution test of the library individual sources showed significant isolate misclassification with an average rate of correct classification (ARCC) of 58%. These misclassifications were explained by low antibiotic resistance (Wilcoxon test P < 0.0001). Seasonal DA of stream E. coli isolates for the pooled sources human/livestock/deer indicated that in fall, the human source dominated (P < 0.0001) at a rate of 56%, and that human and livestock respective contributions in winter (35 and 39%), spring (43 and 40%), and summer (37 and 35%) were similar. Deer scored lower (17–28%) than human and livestock at every season. The DA was revised using results from a misclassification analysis to provide a perspective of the effect caused by low antibiotic resistance and a more realistic determination of the fecal source rates at Turkey Creek. The revision increased livestock rates by 13–14% (0.04 ≤ P ≤ 0.06), and decreased human and deer by 6–7%. Negative misclassification into livestock was significant (0.04 ≤ P ≤ 0.06). Low antibiotic resistance showed the greatest effect in this category.     

Modeling pesticide fate in a small tidal estuary

The exposure analysis modeling system (EXAMS), a pesticide fate model developed by the U.S. Environmental Protection Agency, was modified to model the fate of the herbicides atrazine and metolachlor in a small tidally dominated estuary (Bath Creek) in North Carolina, USA where freshwater inflow accounts for only 3% of the total flow. The modifications simulated the changes that occur during the tidal cycle in the estuary, scenarios that are not possible with the original EXAMS model. Two models were created within EXAMS, a steady-state model and a time-variant tidally driven model. The steady-state model accounted for tidal flushing by simply altering freshwater input to yield an estuary residence time equal to that measured in Bath Creek. The tidal EXAMS model explicitly incorporated tidal flushing by modifying the EXAMS code to allow for temporal changes in estuary physical attributes (e.g., volume). The models were validated with empirical measurements of atrazine and metolachlor concentrations in the estuary shortly after herbicide application in nearby fields and immediately following a rain event. Both models provided excellent agreement with measured concentrations. The steady-state EXAMS model accurately predicted atrazine concentrations in the middle of the estuary over the first 3 days and under-predicted metolachlor by a factor of 2–3. The time-variant, tidally driven EXAMS model accurately predicted the rise and plateau of both herbicides over the 6-day measurement period. We have demonstrated the ability of these modified EXAMS models to be useful in predicting pesticide fate and exposure in small tidal estuaries. This is a significant improvement and expansion of the application of EXAMS, and given the wide use of EXAMS for surface water quality modeling by both researchers and regulators and the ability of EXAMS to interface with terrestrial models (e.g., pesticide root zone model) and bioaccumulation models, we now have an easily-accessible and widely accepted means of modeling chemical fate in estuaries.     

铁铜双金属有机骨架MIL-101(Fe,Cu)活化双氧水降解染料性能

针对非均相芬顿传质效率低和Fe（Ⅲ）Fe（Ⅱ）转化慢导致活性低等问题,采用溶剂热法制备铁铜双金属有机骨架材料[MIL-101（Fe,Cu）],并研究了材料界面性质、催化降解染料（亚甲基蓝）性能以及活化催化机制.结果表明,MIL-101（Fe,Cu）晶体结构完整且呈三维八面体形状;比表面积和平均孔径分别为667.2 m² ·g^-1和1.9 nm,可充分暴露反应活性位点.MIL-101（Fe,Cu）在广谱pH范围可活化H₂ O₂高效降解亚甲基蓝.当pH=5、反应20 min,MIL-101（Fe,Cu）/H₂ O₂对20 mg ·L^-1亚甲基蓝的去除率为100%,较MIL-101（Fe）/H₂O₂和单独H₂ O₂分别提高43.1%和88.9%.自由基猝灭实验与反应前后铁和铜价态变化结果表明,羟基自由基（·OH）是MIL-101（Fe,Cu）/H₂ O₂催化降解亚甲基蓝的主要活性物种;Cu（Ⅱ）掺杂引入新的活性位点,且Cu（Ⅱ）/Cu（Ⅰ）循环和Fe（Ⅲ）/Fe（Ⅱ）循环可协同产生·OH,进而提高催化效率.MIL-101（Fe,Cu）作为新型非均相类芬顿催化剂,无需复杂pH调节即可获得良好催化效果,在工业废水处理上具有较好地应用前景.     

基于LOADEST和数字滤波的水源地基流氮素输出定量方法应用实例

地表直接径流和基流均是流域非点源氮/磷养分输出的重要水文途径.科学认识和定量模拟基流氮/磷养分输出对于准确解析水源地水体非点源污染来源至关重要.基于Load Estimator模型和数字滤波算法,建立了定量水源地基流氮素输出的方法体系.以浙江省珊溪水源地的玉泉溪流域为例,利用玉泉溪2010-01—2013-12期间逐月总氮(TN)水质监测数据和逐日流量数据,展示了该方法的计算过程.结果表明,本文建立的水源地基流氮素输出定量方法结果合理,模拟精度高,决定系数和纳什系数分别为0.83和0.80;玉泉溪流域2010—2013年TN负荷量为141.21～274.68 t·a~(-1),平均208.63 t·a~(-1),年基流TN负荷量为84.39～168.68 t·a~(-1),平均127.69 t·a~(-1);基流对玉泉溪年均TN负荷量贡献率高达60%以上,流域基流养分输出对地表水体的污染应引起足够重视.     

石臼漾人工湿地冬夏季全程氨氧化微生物的分布、群落结构及其影响因素研究

湿地作为水体与陆地之间的过渡地带,具有独特的生态环境特性,是氮循环反应的关键区域.研究湿地生态系统中的全程氨氧化过程（complete ammonia oxidation,comammox）,解析该区域中comammox细菌的分布与群落结构特征,补充了此前该新型氨氧化微生物在湿地生态系统中分布特征的研究空白,对于完善comammox细菌在各种不同生态系统中分布情况的研究具有重要意义.本研究在石臼漾人工湿地中于冬夏两季分别采集了大沟中心、大沟边缘、小沟中心和小沟边缘的表层沉积物样品,利用PCR、荧光定量PCR和amoA功能基因高通量测序等方法,解析人工湿地中comammox细菌的时空分布与群落结构特征.主要研究结果如下：①所有样品中均检测到了comammox细菌,其丰度为1.77×10⁵~4.07×10⁷ copies·g^-1.冬季,comammox细菌丰度在大沟中高于氨氧化细菌（ammonia oxidizing bacteria,AOB）和氨氧化古菌（ammonia oxidizing archaea,AOA）,在小沟中高于AOB,但低于AOA;夏季,comammox细菌丰度在所有样点中均高于AOB和AOA.②冬夏两季样品中,comammox细菌丰度与底物NH₄⁺-N浓度均呈负相关关系,且夏季样品中呈显著性负相关.③主坐标分析（Principle Coordinate Analysis,PCoA）与多样性分析结果表明,comammox细菌群落结构具有空间异质性,且冬季物种多样性高于夏季.     

河岸过滤中氨氮的削减及其浓度对细菌与氨氧化微生物的影响

通过小试滤柱模拟河岸过滤,结合荧光定量PCR和高通量测序等手段研究了河岸过滤对氨氮的削减效能和进水氨氮浓度对细菌与氨氧化微生物的影响.结果表明,低浓度（0.2 mg·L^-1）氨氮未被削减,较高浓度（1.0 mg·L^-1和2.0 mg·L^-1）氨氮的削减率可达70%.进水处细菌丰度随氨氮浓度升高而增加,细菌群落组成随氨氮浓度升高发生规律性变化.出水处氨氧化古菌（Ammonia oxidizing archaea,AOA）丰度与氨氮浓度呈负相关,氨氧化细菌（Ammonia oxidizing bacteria,AOB）丰度与氨氮浓度无显著相关关系;进水处AOA-α多样性与氨氮浓度呈正相关,但AOB-α多样性与氨氮浓度呈负相关;进水处AOA群落组成受氨氮浓度影响,而进、出水处AOB群落组成均受氨氮浓度影响.可见,进水氨氮浓度会影响河岸过滤对氨氮的削减效能,还会影响细菌、氨氧化微生物的丰度及群落结构,AOB对氨氮浓度的变化比AOA更敏感.     

生物质炭强化FeOOH类芬顿催化性能及其机制

采用醇助水热法制备了新型生物质炭修饰的α-FeOOH类芬顿催化剂（BC-FeOOH）,并通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）对催化剂进行了表征,证明生物质炭（BC）成功引入到α-FeOOH中.以罗丹明B（RhB）为目标污染物,考察了BC修饰量、催化剂及H₂O₂投加量对其催化效率的影响.结果表明,BC的引入可以极大地提高FeOOH的类芬顿催化性能.在pH中性、催化剂投加量0.6 g·L^-1、H₂O₂初始浓度10 mmol·L^-1的条件下,BC-FeOOH（22.2% BC）对RhB的降解率可达到90%,重复利用5次活性仍可保持在80%左右,且铁离子溶出浓度仅为0.08 mg·L^-1.进一步通过ESR在不同体系中的测试结果表明,BC的引入不仅可促进H₂O₂有效还原分解产生更多的羟基自由基（·OH）,而且增强了催化剂与污染物RhB的相互作用,促使污染物失电子氧化降解,从而提高了FeOOH的催化活性及催化稳定性.     

铝系混凝剂优势形态分析及其混凝特性

聚合氯化铝（PACl）是常用的水处理混凝剂,在应用过程中通常表现出比传统铝盐更为优异的效果.研究表明,这种优异性能主要得益于其特殊的组成,特别是高分子聚合物Al₁₃和Al₃₀独特的物化特性.Al₁₃和Al₃₀是铝离子水解过程中的中间产物,在地球科学和环境化学等领域有着重要的研究价值.于水处理而言,二者的结构和分子特性是研究者关注的重点,大量研究基于此展开,很多重要的发现为实际应用奠定了基础.基于对PACl及其组成性质的研究,本文对PACl的混凝特性及其优势形态分子的分析进行了综合阐述.