Impact of peroxydisulfate in the presence of zero valent iron on the oxidation of cyclohexanoic Acid and naphthenic acids from oil sands process-affected water

Large volumes of oil sands process-affected water (OSPW) are produced during the extraction of bitumen from oil sands in Alberta, Canada. The degradation of a model naphthenic acid, cyclohexanoic acid (CHA), and real naphthenic acids (NAs) from OSPW were investigated in the presence of peroxydisulfate (S(2)O(8)(2-)) and zerovalent iron (ZVI). For the model compound CHA (50 mg/L), in the presence of ZVI and 500 mg/L S(2)O(8)(2-), the concentration decreased by 45% after 6 days of treatment at 20 °C, whereas at 40, 60, and 80 °C the concentration decreased by 20, 45 and 90%, respectively, after 2 h of treatment. The formation of chloro-CHA was observed during ZVI/S(2)O(8)(2-) treatment of CHA in the presence of chloride. For OSPW NAs, in the presence of ZVI alone, a 50% removal of NAs was observed after 6 days of exposure at 20 °C. The addition of 100 mg/L S(2)O(8)(2-) to the solution increased the removal of OSPW NAs from 50 to 90%. In absence of ZVI, a complete NAs removal from OSPW was observed in presence of 2000 mg/L S(2)O(8)(2-) at 80 °C. The addition of ZVI increased the efficiency of NAs oxidation by S(2)O(8)(2-) near room temperature. Thus, ZVI/S(2)O(8)(2-) process was found to be a viable option for accelerating the degradation of NAs present in OSPW.     

Ozonation of oil sands process-affected water accelerates microbial bioremediation

Ozonation can degrade toxic naphthenic acids (NAs) in oil sands process-affected water (OSPW), but even after extensive treatment a residual NA fraction remains. Here we hypothesized that mild ozonation would selectively oxidize the most biopersistent NA fraction, thereby accelerating subsequent NA biodegradation and toxicity removal by indigenous microbes. OSPW was ozonated to achieve approximately 50% and 75% NA degradation, and the major ozonation byproducts included oxidized NAs (i.e., hydroxy- or keto-NAs). However, oxidized NAs are already present in untreated OSPW and were shown to be formed during the microbial biodegradation of NAs. Ozonation alone did not affect OSPW toxicity, based on Microtox; however, there was a significant acceleration of toxicity removal in ozonated OSPW following inoculation with native microbes. Furthermore, all residual NAs biodegraded significantly faster in ozonated OSPW. The opposite trend was found for ozonated commercial NAs, which are known to contain no significant biopersistent fraction. Thus, we suggest that ozonation preferentially degraded the most biopersistent OSPW NA fraction, and that ozonation is complementary to the biodegradation capacity of microbial populations in OSPW. The toxicity of ozonated OSPW to higher organisms needs to be assessed, but there is promise that this technique could be applied to accelerate the bioremediation of large volumes of OSPW in Northern Alberta, Canada.     

Evaluation of membrane fouling for in-line filtration of oil sands process-affected water: the effects of pretreatment conditions

Membrane filtration is an effective reclamation option for oil sands process-affected water (OSPW). However, fresh OSPWs contain suspended solids and inorganic constituents in suspended and dissolved forms that can severely foul membranes. Pretreatment of OSPW with coagulation-flocculation (CF) was investigated to determine the effects of different coagulant aids (anionic, cationic, and nonionic polymers) on membrane surface properties and fouling. Our results showed that CF pretreatment effectively enhanced nanofiltration (NF) and reverse osmosis (RO) membrane permeate flux and salt rejection ratio through reducing membrane fouling. It was shown that coagulants and coagulant aids applied to OSPW feedwater can affect membrane physicochemical properties (surface hydrophilicity, zeta potential, and morphology), membrane performance, and the fouling indexes. Membrane rejection of ionic species increased significantly with the inclusion of an anionic coagulant aid and slightly with a cationic coagulant aid. Among three coagulant aids tested, anionic coagulant aids led to the most enhanced membrane performance through increasing membrane surface negativity and decreasing the formation of a fouling layer. Conversely, although cationic coagulant aids were the most effective in reducing OSPW turbidity, the application of cationic coagulant aids promoted the adsorption of foulants on membrane surfaces.     

Effect of ozonation on the estrogenicity and androgenicity of oil sands process-affected water

There is increasing environmental concern about the volume of oil sands process-affected water (OSPW) produced by the oil sands industry in Alberta, Canada. There is limited knowledge of the toxic effects of OSPW and one of the primary organic constituents, naphthenic acids (NAs), which are thought to be one of the toxic constituents of OSPW. OSPW and NAs can have endocrine disrupting potential. The NAs in OSPW are persistent, but ozonation can significantly reduce concentrations of NA, while increasing their biodegradability, and consequently reduce OSPW toxicity. However, it is of concern that OSPW ozonation might generate hydroxylated cycloaliphatics with endocrine disrupting potential. In this study, the estrogen receptor- (ER) and androgen receptor- (AR) mediated effects of OSPW and ozone-treated OSPW were investigated in vitro by use of T47D-kbluc (estrogen responsive) and MDA-kb2 (androgen responsive) cells. Ozonation neither attenuated nor intensified the estrogenicity of OSPW. The estrogenic responses to untreated OSPW and ozone treated OSPW were 2.58(±0.22)-fold and 2.48(±0.13)-fold greater than those of controls, respectively. Exposure to untreated OSPW produced significant antiandrogenicity in the presence of 0.01, 0.05, or 0.1 nM testosterone (T), while ozone-treated OSPW produced significant antiandrogenicity in the presence of 0.01 or 0.05 nM T. Exposure to untreated and ozone-treated OSPW also caused potentiation of androgen receptor-mediated effects of T. OSPW could cause estrogenic and antiandrogenic effects through receptor mediated pathways, and ozonation can partially mitigate the OSPW antiandrogenicity as well as androgen potentiating effect, without increasing estrogen potency.     

Structure-reactivity of naphthenic acids in the ozonation process

Large volumes of oil sands process-affected water (OSPW) are produced in northern Alberta by the surface mining oil sands industry. Naphthenic acids (NAs) are a complex mixture of persistent organic acids that are believed to contribute to the toxicity of OSPW. In situ microbial biodegradation strategies are slow and not effective at eliminating chronic aquatic toxicity, thus there is a need to examine alternative remediation techniques. NAs with multiple rings and alkyl branching are most recalcitrant to microbial biodegradation, but here we hypothesized that these same structural features may lead to preferential degradation in the ozonation process. Total NA degradation increased with increasing pH for commercial NA solutions, suggesting a hydroxyl radical mechanism and that naturally alkaline OSPW would unlikely require pH adjustment prior to treatment. For commercial NAs and OSPW, NAs with more rings and more carbon (and more H atoms) were depleted most rapidly in the process. Relative rate measurements with binary mixtures of model NA compounds not only confirmed this structure reactivity but also indicated that alkyl branching patterns were an additional factor determining NA reactivity. The results demonstrate that ozonation is complementary to microbial biodegradation, and the process remains a promising water reclamation strategy for the oil sands industry.     

Influence of molecular structure on the biodegradability of naphthenic acids

Large volumes of toxic aqueous tailings containing a complex mixture of naphthenic acids (NAs; CnH2n+ZO2) are produced in northern Alberta by the oil sands industry. Because of their persistence and contribution to toxicity, there is an urgent need to understand the fate of NAs under a variety of remediation scenarios. In a previous study, we developed a highly specific HPLC-high resolution mass spectrometry method for the analysis of NAs. Here we apply this method to determine quantitative structure-persistence relationships and kinetics for commercial NAs and NAs in oil sands process water (OSPW) during aerobic microbial biodegradation. Biodegradation of commercial NAs revealed thatthe mixture contained a substantial labile fraction, which was rapidly biodegraded, and a recalcitrant fraction composed of highly branched compounds. Conversely, NAs in OSPW were predominantly recalcitrant, and degraded slowly by first-order kinetics. Carbon number (n) had little effect on the rate of biodegradation, whereas a general structure-persistence relationship was observed indicating that increased cyclization (Z) decreased the biodegradation rate for NAs in both mixtures. Time to 50% biodegradation ranged from 1 to 8 days among all NAs in the commercial mixture, whereas half-lives for OSPW NAs ranged from 44 to 240 days, likely a result of relatively high alkyl branching among OSPW NAs. It is anticipated that these data will facilitate development of strategic solutions for remediating billions of cubic meters of OSPW stored, or predicted to be generated, in Northern Alberta.     

Effectiveness of ozonation treatment in eliminating toxicity of oil sands process-affected water to Chironomus dilutus

Water soluble organic compounds (OCs), including naphthenic acids (NAs), are potentially toxic constituents of oil sands process-affected water (OSPW) that is generated during extraction of bitumen from Alberta oil sands. Ozonation can decrease concentrations of OCs in OSPW. However, effects of ozonated-OSPW on multicellular organisms are unknown. A 10-day and a chronic exposure of Chironomus dilutus to OSPW were conducted to assess effects on survival, growth, development, and behavior. Two separate batches of OSPW were treated with 30 or 80 mg ozone (O(3))/L. Wet body masses of larvae exposed to OSPW were 64 to 77% less than their respective controls (p < 0.001). However, both levels of ozonation significantly attenuated effects of OSPW on growth. Similarly, chronic exposure to untreated OSPW resulted in significantly less pupation than in the controls, with 31% and 71% less pupation of larvae exposed to the two batches of OSPW (p < 0.05). Emergence was significantly less for larvae exposed to OSPW, with 13% and 8% of larvae emerging, compared to 81% in controls (p < 0.0001). Both levels of ozonation of OSPW attenuated effects on emergence. These results suggest that OCs degraded by ozonation causes toxicity of OSPW toward C. dilutus, and that ozonation attenuates toxicity of OSPW.     

Stability and removal of water soluble CdTe quantum dots in water

Commercial use of quantum dots (GDs) will lead to their entry into aquatic environments. This study examines the characteristics and stability of CdTe QDs with thioglycolate capping ligands in water as well as their removal by alum salts. The capping ligands of QDs are a key factor in determining their fate in water. Protonated thioglycolate capping ligands cause QDs to aggregate. The stability of QDs depends more on their ionic composition in water than on the ionic strength. In KCl solution, QDs remain stable even under 0.15 M ionic strength. Relatively low concentrations (< or = 2 meq/L) of divalent (Mg2+ and Ca2+) or trivalent (Al3+) cations, however, can induce aggregation. The proposed mechanism for this phenomenon is that multivalent metal cations (or their hydrated species) react with capping ligands to form complexes that bridge QDs or neutralize their surface charges. Because the complexation of hydrated Al3+ with capping ligands inhibits the formation of Al(OH)3 precipitates, alum dosages higher than the A3+ solubility are required to form settleable flocs and remove QDs from nanopure water by sedimentation. Divalent cations (Mg2+ and Ca2+) in tap water induce the formation of settleable QD flocs such that 70-80% of the QGDs by mass settle out.     

盐渍海蜇加工过程中铝的变化规律研究

目的以鲜海蜇为原料,研究三矾工艺加工盐渍海蜇过程中铝的含量及其形态变化,为盐渍海蜇中铝的控制与安全性评价提供依据。方法以溶液浸取法提取海蜇样品中不同形态的铝,采用电感耦合等离子体质谱仪(ICP-MS)测定各形态铝的含量。结果在加工过程中海蜇的总铝含量逐渐增加,鲜海蜇、初矾、二矾、三矾海蜇中总铝含量分别为12.10 mg/kg、99.80 mg/kg、440.04 mg/kg、701.49 mg/kg;海蜇中铝的主要形态为无机态铝,有机态铝的含量较低,鲜海蜇、初矾、二矾、三矾海蜇中无机态铝占总铝的比例依次为70.83%、79.41%、86.16%、93.10%;无机态铝中大部分为沉淀态的Al(OH)_3,在海蜇样品中均占总铝含量的50%以上。结论采用传统三矾工艺加工盐渍海蜇,海蜇中铝的含量显著增加,其中铝的形态主要为无机态。因此,盐渍海蜇铝毒性的大小可直接用总铝含量来评价。     

Pilot scale comparison of enhanced coagulation with magnetic resin plus coagulation systems

Previous work has shown that magnetic ion-exchange treatment before coagulation gives high natural organic matter (NOM) removal and reduced levels of disinfection byproduct when compared to conventional enhanced coagulation. The impact of the resin process on the downstream floc formation process after coagulation and the subsequent effect on clarification has not previously been shown. Water containing high concentrations of NOM were treated at pilot scale using (1) conventional enhanced coagulation and compared with (2) treatment using magnetic resin followed by coagulation at reduced doses of 50-70%. Bench scale testing was also carried out to determine floc properties for systems with and without resin pretreatment It was demonstrated that pretreatment using magnetic resin was able to significantly reduce the turbidity load onto filters as a result of the formation of a large and more robust floc. Resin pretreatment also improved NOM removal and reduced disinfection byproduct formation when compared with conventional coagulation. The turbidity load on to the filters following resin pretreatment was 1.5 +/- 0.7 NTU, whereas this value was 2.9 +/- 0.3 NTU for conventional coagulation. Flocs produced with resin pretreatment were larger than those produced by conventional coagulation, with a median floc size of 1000 microm compared to 600 microm. The improvement in floc properties following magnetic resin pretreatment was proposed to be due to the removal of NOM thatwas characteristic of carboxylic acids before the coagulation stage.     

滤纸中增强乳液树脂热迁移的研究

针对滤纸中增强乳液树脂在干燥过程中的热迁移现象进行了较为系统的研究。探讨了明矾与带正电荷的水溶性聚合物复配体系对阻碍增强树脂热迁移的作用。并通过纸页层间剪切强度、滤纸的扫描电子显微镜(SEM)图像等对处理后的滤纸热迁移程度与增强后的纸页各项性能进行了表征。     

Stoichiometry of coagulation revisited

The roles of particles and natural organic matter (NOM) in determining coagulant (alum) doses in potable water treatment were investigated at two pH conditions (6 and 7). The concentrations of NOM and colloidal silica particles in raw water were systematically varied separately and in combination, and the impacts of these two classes of contaminants on the minimum effective alum doses were investigated using observations of turbidity and dissolved organic carbon (DOC) in laboratory jar tests. At both pHs, coagulant requirements for the removal of these contaminants by sedimentation and filtration were dominated by the DOC concentration in the raw water. The presence of low NOM concentrations (0.75-1.5 mg of C/L) decreased the minimum effective alum dose dramatically for waters low in silica particles, possibly by promoting the precipitation of aluminum hydroxide and/or Al-NOM solids, whose removal would otherwise be limited by low collision opportunities. Strong stoichiometric relationships were observed between DOC and coagulant demand at both pHs regardless of silica particle concentration. Silica contributed to coagulant demand only at very high particle concentrations.     

阻燃植物纤维模塑墙体装饰材料的制备

通过阳离子淀粉预处理氢氧化铝来制备阻燃植物纤维模塑墙体装饰材料。实验研究表明,阳离子淀粉预处理氢氧化铝后增大了其粒径;随着阳离子淀粉用量的增加,墙体装饰材料的灰分显著增加,采用预处理工艺得到的材料灰分增加得更明显,当阳离子淀粉用量为1.5%时,预处理中添加和普通植物纤维纸浆内添加的墙体装饰材料的灰分均达到最大值,分别为19.9%和19.3%。还探讨了预处理工艺对植物纤维墙体装饰材料挺度的影响,在提高阻燃剂留着率的同时,也对纸浆滤水性能进行了探讨,最后利用热重分析、SEM等方法探讨了阻燃机理。     

Assessing natural organic matter treatability using high performance size exclusion chromatography

This paper reports the use of high performance size exclusion chromatography (HPSEC) as a tool to assess NOM removal by coagulation. Quantitative information such as percentage removal can be determined after "peak-fitting" the HPSEC molecular weight profile of the source water. A peak-fitting approach was developed based on the molecular weight profile of dissolved organic matter from surface water. A sequential jar testing procedure with five treatment steps was used to characterize organics and to confirm that several NOM components were recalcitrant to coagulation with alum. Despite differences found in both the concentration and character of NOM in three surface waters studied, the final concentrations and characteristics (e.g., molecular weight profile) were very similar after five treatment stages. The molecular weight profiles of the recalcitrant organics were subsequently used to build a peak-fitting technique for NOM removal. The approach was validated by further jar test results of several other water sources, such as ground and river waters, including one found to be very difficult to treat in terms of NOM removal by alum treatment. Predictions of removable and nonremovable organic fractions by coagulation using this peak fitting technique were found to be within 10% of actual values.     

Selective coagulant recovery from water treatment plant residuals using Donnan membrane process

Fouling of membrane surfaces by particulate matter and large organic molecules is relatively common for pressure-driven membrane processes, namely, reverse osmosis (RO), nanofiltration (NF), and ultrafiltration (UF). Donnan membrane process (DMP) or Donnan Dialysis is driven by electrochemical potential gradient across a semipermeable ion exchange membrane. Theoretically, DMP is not susceptible to fouling by fine particulates and/or large organic molecules. According to information available in the open literature, however, DMP has not been tried to treat slurry or sludge with relatively high concentration of suspended solids or large organic molecules. This study presents the salient results of an extensive investigation pertaining to selective alum recovery from water treatment residuals (WTR) using DMP. Water treatment plants use alum, Al2(SO4)3 x 14H2O, as a coagulant, alum being finally converted and discharged as insoluble aluminum hydroxide along with natural organic matters (NOM), suspended solids, and other trace impurities. One commercial cation exchange membrane, namely Nafion 117 from DuPont Chemical Co., was used in the study for treating WTR obtained from two different water treatment plants in Pennsylvania. A series of laboratory tests confirmed that over 70% of alum is easily recoverable, and recovered alum is essentially free of particulate matter, NOM, and other trace metals. Most importantly, after repeated usage in the presence of high concentration of NOM and suspended solids, there was no noticeable decline in aluminum flux through the membrane, i.e., membrane surface fouling was practically absent. The DMP process involves coupled transport of Al3+ and H+ across the cation exchange membrane, and intramembrane transport was the rate-limiting step. Experimentally determined aluminum-hydrogen interdiffusion coefficient (D(Al-H)) values within the membrane were quite high (approximately 10(-6) cm2/s) under representative conditions, thus confirming high alum recovery rate. DMP was also found equally effective in recovering Fe(III) based coagulants from WTR.     

分形分析GCC絮体结构特征及其对手抄片性能的影响

重质碳酸钙加入浆中前对其进行絮凝,在提高其添加量的同时尽可能使纸张强度降低最小。填料絮体特性,如絮体粒径、结构对絮凝效果有较强的影响。本文使用质量分形分析方法来确定絮体结构对絮凝系统的影响,利用光衍射光谱得到三种不同絮凝剂体系在高剪切条件下絮凝的絮体质量分析维数。该三种絮凝剂体系分别为单聚合物C-PAM、双阳离子聚合物p-DADMAC/C-PAM、大聚合物组合C-PAM/大聚合物,采用这三种絮凝剂体系对填料进行絮凝,絮凝后加到浆中抄成手抄片,然后研究其对手抄片性能的影响。研究发现,经C-PAM/大聚合物絮凝的GCC加填后的手抄片抗张指数得到了最大的改善。从质量分形分析结果可知,这是由于该絮凝剂体系使填料在絮凝过程中形成絮体更紧密,更接近于球形。手抄片截面分析也表明,采用C-PAM/大聚合物絮凝剂体系絮凝GCC絮体具有更均一的粒径。综上所述,分形分析能使我们更好地理解絮凝填料的特性和它们对纸张性能的影响：加填填料絮体越致密,越接近于球形,越有利于改善抄造纸张的抗张指数。     

e—CDP／CPAM／MMT三元体系控制废纸浆DCS的作用与效果

研究了阳离子环糊精聚合物（C-CDP）作为固着剂在控制废纸浆DCS的作用,结果表明其对溶解物质和胶体物质具有很好的去除效果,当用量为1％时,浊度、阳离子需求量和COD分别减少了98．67％、95％和48．17％。研究TC-CDP／CPAM／MMT体系在控制废纸浆DCS的协同作用,结果表明：C-CDP／CPAM／MMT三元体系对控制废纸浆DOS具有很好的协同作用,在C—CDP用量0．2％、CPAM用量0．1％、MMT用量0．2％时,废纸浆的Zeta电位绝对值逐渐减小,滤水性能提高45．06％,电导率下降约4．57％,阳离子需求量和浊度显著下降。     

利用FBRM研究阳离子聚丙烯酰胺对高岭土的动态絮凝过程

利用聚焦光束反射测量仪（FBRM）研究了阳离子聚丙烯酰胺（CPAM）对高岭土颗粒体系的动态絮凝过程,结合浊度仪、激光衍射粒度仪、显微摄像等表征手段,探讨了絮凝剂用量对絮凝性能和絮体结构的影响。同时基于分形理论对絮凝过程中絮体分形维数的变化进行了考察,基于Smoluchowski模型研究了CPAM作用下高岭土粒子的絮凝动力学。结果表明,随着药品用量的增加,体系中粒子的平均弦长和粒径逐渐增大,体系达到稳定的时间延长,浊度不断下降。在絮凝过程中,随着作用时间的延长,絮体结构发生变化,分形维数增加,形成相对致密的絮体。增加絮凝剂的用量,絮凝作用增强,絮体尺寸变大,絮凝速率较快,需较长的絮凝反应时间才能达到平衡。     

As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.