绿色絮凝剂PAS的性能及混凝机理探讨

通过向聚硅酸中加入一种高价亲生物环保的金属离子Ti⁴⁺，制备了一种适合处理长江水的绿色絮凝剂PAS，并且通过实验确定了其处理长江水的最佳处理条件：酸性聚硅酸与Ti金属盐溶液复合，n_Ti/n_Si=0.3；投加量为10 mg/L（以Ti⁴⁺计），pH=6～8，UV254的去除率＞61.7％，浊度去除率＞99％。PAS的混凝效果明显优于聚合铝和聚硅铝，而且矾花形成迅速，絮体密实、沉降快、出水更加清澈，无残留铝。Ti也是亲生物金属，健康环保。因此，PAS是绿色环保友好型絮凝剂，可作为饮用水专用絮凝剂。观察所形成絮体的形貌以及观测红外光谱图均发现，絮凝剂对胶体颗粒污染物有较好的架桥网捕与络合反应作用。     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料，通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS），研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响，用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L，硅酸活化时间为2 h，Si∶Al∶Zn=1∶1∶1.5，絮凝剂投加量为20 mL/L废水时，絮凝剂的电中和能力和吸附架桥能力最强，絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

Fenton-聚硅铝铁硼处理生活垃圾压滤液研究

以正交设计方法为基础，以COD去除率为指标，确定了聚硅铝铁硼（PSAFB）最优制备条件，研究了Fenton-PSAFB混凝法处理城市生活垃圾压滤液的最优反应条件和处理效果。结果表明：以200 mL生活垃圾压滤液为处理对象，复合絮凝剂PSAFB的最优制备工艺条件为：Al/Si为1/2，Fe/Si为1/2，B/Si为1/6；其最优反应条件为：pH值为5.0，投加量为200 mg/L（以SiO₂计)；Fenton法最优反应条件为：pH值为3.0，30%H₂O₂为20 mL，1 mol/L FeSO₄为30 mL；采用最优反应条件的Fenton-PSAFB处理垃圾压滤液，浊度去除率达到95.2%，COD去除率达到84.2%，BOD₅去除率达到81.5%。     

聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

混凝工艺去除合流污水中有机物及营养元素

通过系列杯罐试验混凝处理合流污水，采用硫酸铝（Al₂(SO₄)₃）、硫酸铁（Fe₂(SO₄)₃）、聚合氯化铝（PAC）和聚合氯化铝铁（PAFC）4种混凝剂均能有效去除污水中的 TP、PO^3-₄-P、SS和COD。聚合金属盐（PAC和PAFC）混凝处理效果优于金属盐（Al₂(SO₄)₃和Fe₂(SO₄)₃），达到相同的处理效果的投加量明显低于后者。助凝剂采用聚丙烯酰胺（PAM）、聚乙烯醇（PVA）、自制的高分子聚合物（AN）和活化硅酸（AS），在保持较低混凝剂投加量的条件下可明显提高污水处理效果；添加助凝剂对强化PO^3-₄-P的去除作用不明显，PO^3-₄-P的去除仅与混凝剂的投加量相关。混凝剂和助凝剂对污水中NH₃-N的去除作用相对不显著。SS去除率随混凝剂投加量的变化趋势说明混凝的机理较为复杂，可能存在多种混凝机理共同作用。     

废弃印刷线路板碘化法浸金研究

针对碘化法从废弃印刷线路板中提取金的工艺设计，分别考察了碘的质量分数、n(I₂)/n(I^-)比值、固液比、双氧水的质量分数、pH值、浸出时间和浸出温度对金浸出率的影响。结合正交设计优化实验方法,提出了从废弃印刷线路板中碘化法浸取金的最佳工艺条件：碘的质量分数为1.1％，n(I₂)∶n(I^-)=1∶10，双氧水的质量分数为1.5％，浸出时间4 h，固液比为1∶10，浸出温度为常温（25℃），溶液pH值为中性，此时金浸出率可达97.5％。     

锰掺杂WO3-TiO2复合光催化剂的制备及其性能研究

溶胶-凝胶和浸渍相结合的方法制备锰掺杂WO₃-TiO₂复合光催化剂，RXD表征，考察WO₃和Mn²⁺掺入量、焙烧温度、焙烧时间及催化剂用量对光催化降解甲基橙的影响。结果表明，500℃焙烧2h，掺杂量n_{（Mn²⁺）}∶n_（WO3）∶n_（TiO2）＝0.8∶1∶100时，光催化活性最高，光催化降解甲基橙溶液，120min后，降解率达90%, 比单纯 TiO₂的光催化活性提高81%。     

O3/BAF工艺系统中有机物生物降解数学模型

研究臭氧预氧化/曝气生物滤池（O₃/BAF）联合工艺深度处理实际城市污水二级出水过程中，后续BAF系统中有机物的生物降解数学模型。以有机底物浓度、填料层高度两个基本变量为控制条件，研究BAF的总体运行常数和填料特性常数,得出BAF有机物生物降解动力学方程为S_e/S₀=exp(－Kh/qSⁿ₀)。出水与进水COD浓度比值（S_e/S₀）的对数与反应器填料高度（h）之间可表达成一次函数关系。在不同的进水浓度（S₀）下，根据ln（S_e/S₀）~h和关系式m=K/qSⁿ₀，得到方程ln(q_m)=－nln(S₀)+lnK。BAF总体运行常数K和填料特性常数n分别为1.708和0.5063。该模型对BAF工艺有如下指导意义：可以根据设计流量、进水有机物浓度和出水浓度，初步确定BAF的尺寸（如横截面积、高度等）。     

微波-Fenton 氧化-PAFSi 絮凝法处理含油废水简

采用微波-Fenton氧化-PAFSi絮凝法处理含油废水，结果表明，200 mL水样先经微波辐射6 min，在pH=2，H₂O₂（30%）3.5 g/L，Fe²⁺ 1.3 g/L的条件下氧化4 h后，采用聚硅酸铝铁（Al：Fe：Si=10：2：1）和聚丙烯酰胺在pH=8时进行絮凝实验，处理后废水浊度、SS、COD、含油量和色度分别降低了99.46%、96.66%、91.94%、97.97%和95.00%，且经处理后废水的BOD₅/COD由原水的0.04提高到0.53。实验还分析了含油废水的降解机理。     

钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态，降低其在土壤中的有效浓度、植物毒性及生物有效性，影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明，HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量，有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性，增加了烟草叶中Cd的吸收量，有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看，HA最适合应用于烟草植物修复铅镉污染土壤。     

响应面分析法优化稀土废水MAP沉淀法脱氮

经过预处理后的稀土生产废水，其氨氮浓度大幅降低，但并未达到中华人民共和国《稀土工业污染物排放标准》（GB26451-2011）中氨氮浓度限值。实验通过响应面分析法中的Box-Behnken实验设计（BBD），取pH、n（Mg）：n（N）、n（P）：n（N）3因素，采用Design-Expert 8.0.6，建立合适的剩余氨氮浓度及剩余总磷浓度模型，得到回归方程，并分析模型各项指标，各因素及其相互作用对剩余氨氮浓度及剩余总磷浓度的影响。利用预测模型预测最佳实验条件，在最佳实验条件下验证预测结果，并对沉淀物进行X射线衍射（XRD）分析。结果显示，二次响应模型适用于剩余氨氮浓度及剩余总磷浓度，2个模型均拥有较好的拟合程度、可信度及精密度，最优反应条件为：pH=9.88、n（Mg）：n（N）=1.50：1、n（P）：n（N）=1.38：1时，剩余氨氮浓度为46.58 mg/L，剩余总磷浓度为7.85 mg/L。在最优条件下所得到的沉淀物并非纯净的MgNH₄PO₄·6H₂O，还有Mg₃（PO₄）₂·22H₂O生成。     

Source apportionment of time and size resolved ambient particulate matter measured with a rotating DRUM impactor

Ambient particulate chemical composition data acquired from samples collected using a three-stage Davis Rotating-drum Universal-size-cut Monitoring (DRUM) impactor in Detroit, MI, between February and April 2002 were analyzed through the application of a three-way factor analysis model. PM_2.5 (particulate matter ⩽2.5 μm in aerodynamic diameter) was collected by a DRUM impactor with 3-h time resolution and three size modes (2.5 μm>D_p>1.15 μm, 1.15 μm>D_p>0.34 μm and 0.34 μm>D_p>0.1 μm). A novel three-way factor analysis model was applied to these data where the source profiles are a three-way array of size, composition and source while the contributions are a matrix of sample by source. Nine factors were identified: road salt, industrial (Fe+Zn), cloud processed sulfate, two types of metal works, road dust, local sulfate source, sulfur with dust, and homogeneously formed sulfate. Road salt had high concentrations of Na and Cl. Mixed industrial emissions are characterized by Fe and Zn. The cloud processed sulfate had a high concentration of S in the intermediate size mode. The first metal works represented by Fe in all three size modes and by Zn, Ti, Cu, and Mn. The second included a high concentration of small size particle sulfur with intermediate size Fe, Zn, Al, Si, and Ca. Road dust contained Na, Al, Si, S, K, and Fe in the large size mode. The local and homogeneous sulfate factors show high concentrations of S in the smallest size mode, but different time series behavior in their contributions. Sulfur with dust is characterized by S and a mix of Na, Mg, Al, Si, K, Ca, Ti, and Fe from the medium and large size modes. This study shows that the utilization of time and size resolved DRUM data can assist in the identification of sources and atmospheric processes leading to the observed ambient concentrations.     

The chemical species distribution and transformation of polyaluminum silicate chloride coagulant

The chemical species distributions of polyaluminum silicate chloride (PASC) and polyaluminum chloride (PACl) determined by Al-Ferron complexation timed spectrophotometric and 27Al-NMR methods, respectively, have been compared and analyzed. The experimental results show that the species distribution and transformation of PASC are different from those of PACl, due to the interaction of polysilicic acid and hydrolyzed aluminum species. At the same basicity (B), the contents of, Al(b), Al13 and the monomer species Almono (also determined by 27Al-NMR) in PASC are lower than those in PACl, while the contents of Al(c) and the Alother determined by 27Al-NMR in PASC are higher than those in PACl. The differences between PASC and PACl with respect to these species enlarge as the molar ratio of Al/Si in PASC decreases. Further, in PACl the ratio of Al13 to Al(b) closes to 1.0, indicating that the amount of the two fractions are similar. In PASC, however, such an agreement does not exist at the lower B values and Al/Si molar ratios. When the B value and Al/Si molar ratios increase, however, the amount of Al13 and Al(b) species tends to close. The study findings indicate that polysilicic acid can react with hydrolyzed aluminum species to form an aluminum silicate polymer composite and result in the change in species distribution of PASC.     

Fenton-混凝法处理苯胺废水

农药生产过程中产生的苯胺废水,COD浓度高、生物毒性强、可生化性差,一般生化方法很难处理。研究了Fenton与PAC联用处理苯胺废水。结果表明,Fenton氧化处理苯胺废水在最佳条件为pH=6、m（H2O2）/m（COD）=1.8、n（H2O2）/n（Fe2＋）=8时,COD和色度去除率分别为78.4%和92.3%。Fenton氧化后废水B/C值由0.037提高到0.324。最佳条件下联用PAC,在投加量为320 mg/L时COD与色度去除率分别为83.6%和94.8%,并且处理时间显著缩短,实际应用中可减少水力停留时间和构筑物体积。     

模拟阳光下Ag/I-TiO_2光催化预处理山核桃加工废水

研究了在模拟太阳光下,采用银修饰的碘掺杂二氧化钛光催化剂(Ag/I-TiO2)对某食品厂山核桃加工废水进行光催化预处理的效果。结合X射线衍射(XRD)、比表面积分析(BET)、紫外-可见漫反射光谱(UV-Vis)的表征结果,来分析催化剂结构对于废水处理效果的影响。探讨了Ag含量、废水初始pH(pHi)和光照时间等因素对化学需氧量(COD)去除及水质可生化性(B/C)提高的影响。并得出适宜的反应参数为:3%Ag含量;pHi为6;光照时间为240 min。在最佳条件下,COD去除率45%,废水B/C比由0.17上升到0.31。光催化氧化法能够有效降低山核桃加工废水的COD含量,并达到显著提高废水可生化性的目的。     

纳米聚硅酸铝锌絮凝剂的制备及表征简

在SiO₂含量为3%，pH为3，活化时间为85 min，（Al+Zn ）/Si摩尔比为1.5，Al/Zn摩尔比为2，表面活性剂硬脂酸钠加入量为0.1%，超声频率为40 Hz，超声时间为60 min的最佳制备条件下制备出液体PSAZS絮凝剂，用超声法制成纳米级Nano-PSAZS，用环境扫描电子显微镜（ESEM）和智能型傅里叶变换红外光谱（FT-IR）等仪器进行分析。结果表明，硅有助于絮凝剂分子链的延伸，有助于生成更大分子的聚合物；铝盐和锌盐的加入到聚硅酸中，并不是简单的混合，而是发生了缩聚和配位反应，有助于生成链网状结构，能更好地发挥吸附架桥和网捕卷扫作用。同时Nano-PSAZS陈化时间为24 h时的结构有利于絮凝效果的发挥。     

Evaluation of airborne particulate matter and metals data in personal,indoor and outdoor environments using ED-XRF and ICP-MS and co-located duplicate samples

Factors and sources affecting measurement uncertainty associated with monitoring metals in airborne particulate matter (PM) were investigated as part of the Windsor, Ontario Exposure Assessment Study (WOEAS). The assessment was made using co-located duplicate samples and a comparison of two analytical approaches: ED-XRF and ICP-MS. Sampling variability was estimated using relative percent difference (RPD) of co-located duplicate samples. The comparison of ICP-MS and ED-XRF results yields very good correlations (R² ≥ 0.7) for elements present at concentrations that pass both ICP-MS and ED-XRF detection limits (e.g. Fe, Mn, Zn, Pb and Cu). PM concentration ranges (median, sample number) of 24-h indoor PM₁₀ and personal PM₁₀ filters, and outdoor PM_2.5 filters were determined to be 2.2–40.7 (11.0, n = 48) μg m^?3, 8.0–48.3 (11.9, n = 48) μg m^?3, and 17.1–42.3 (21.6, n = 18) μg m^?3, respectively. The gravimetric analytical results reveal that the variations in PM mass measurements for same-day sampling are insignificant compared to temporal or spatial variations: 92%, 100% and 96% of indoor, outdoor and personal duplicate samples, respectively, pass the quality criteria (RPD ≤ 20%). Uncertainties associated with ED-XRF elemental measurements of S, Ca, Mn, Fe and Zn for 24-h filter samples are low: 78%–100% of the duplicate samples passed the quality criteria. In the case of 24-h filter samples using ICP-MS, more elements passed the quality criteria due to the lower detection limits. These were: Li, Na, K, Ca, Si, Al, V, Fe, Mn, Co, Cu, Mo, Ag, Zn, Pb, As, Mg, Sb, Sn, Sr, Th, Ti, Tl, and U. Low air concentrations of metals (near or below instrumental detection limits) and/or inadvertent introduction of metal contamination are the main causes for excluding elements based on the pass/fail criteria. Uncertainty associated with elemental measurements must be assessed on an element-by-element basis.     

Major to ultra trace elements in rainfall collected in suburban Tokyo

Major to ultra trace elements such as rare earth elements (REEs), platinum group elements (PGEs) in 20 rainfall events from suburban Tokyo were determined by inductively coupled plasma mass spectrometry (ICP-MS). Anion species were also determined by an ion chromatography (IC). The concentrations of PGEs were so low that only Pt was detected in some rainfall events. Enrichment factors (EFs), refer to soil and sea salt components, were calculated for the measured elements (with Al and Na as references). Be, (Na), Mg, (Al), Si, Cl, K, Fe, Rb, Sr, REEs (except La, Gd), Ta, and U were mostly originated from natural materials (soil and sea salt). For Li, B, Ca, Mn, Sr, Ba, and Cs, the contribution of natural materials was significant. EFs for Cu, Zn, As, Se, Sb, Cd, Pb, Bi, Ag, Te, Au, Pt, SO₄-S and NO₃-N exceeded 100 indicating non-crustal, non-sea salt origin, presumably anthropogenic; however, contribution of volcanic gases could not be excluded for As, Se, Te and Bi. Pt seemed to be uniformly distributed worldwide and a catalyst for automobile emission control may be the main source. Au also showed uniform distribution. On the other hand, EFs for Zr, Nb, Hf and Th were less than unity. Probably these elements resided in acid resistant refractory fine minerals that did not decompose with acid treatment, and did not evaporate and ionize in the ICP. An alternative explanation is that the concentration of these elements was lower in the soil of the sampling area than the average crust. In the crust normalized REE pattern plot, La, Eu and Gd showed clear positive anomalies. La and Gd could have anthropogenic components. A possible source of La and Gd is cracking catalyst for petrol refining, but this source does not fully explain the anomaly. The source of Gd may also be Gd-DTPA (Gadolinium (III) diethyltriaminepentaacetic acid) used for Magnetic Resonance Imaging (MRI) contrast agents. The Eu origin may be soil with higher concentration than the crust average.