Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences, Box 7050, Uppsala, Sweden.
Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences, Box 7050, Uppsala, Sweden.
Water Res. 2016 Feb 1;89:232-40. doi: 10.1016/j.watres.2015.11.048. Epub 2015 Nov 27.
Rising organic matter concentrations in surface waters in many Nordic countries require current drinking water treatment processes to be adapted. Accordingly, the use of a novel nanofiltration (NF) membrane was studied during a nine month period in pilot scale at a large drinking water treatment plant in Stockholm, Sweden. A chemically resistant hollow-fibre NF membrane was fed with full scale process water from a rapid sand filter after aluminum sulfate coagulation. The combined coagulation and NF process removed more than 90% of the incoming lake water dissolved organic carbon (DOC) (8.7 mg C L(-1)), and 96% of the absorbance at 254 nm (A254) (0.28 cm(-1) incoming absorbance). Including granulated active carbon GAC) filter, the complete pilot plant treatment process we observed decreases in DOC concentration (8.7-0.5 mg C L(-1)), SUVA (3.1-1.7 mg(-1) L m(-1)), and the average nominal molecular mass (670-440 Da). Meanwhile, water hardness was practically unaffected (<20% reduction). Humic substances (HS) and biopolymers were almost completely eliminated (6510-140 and 260 to 10 μg C L(-1) respectively) and low molecular weight (LMW) neutrals decreased substantially (880-190 μg C L(-1)). Differential excitation emission matrices (EEMs), which illustrate the removal of fluorescing organic matter (FDOM) over a range of excitation and emission wavelengths, demonstrate that coagulation removed 35 ± 2% of protein-like material and 65 ± 2% of longer emission wavelength, humic-like FDOM. The subsequent NF treatment was somewhat less selective but still preferentially targeted humic-like FDOM (83 ± 1%) to a larger extent than protein-like material (66 ± 3%). The high selectivity of organic matter during coagulation compared to NF separation was confirmed from analyses with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and liquid chromatography with organic carbon detection (LC-OCD), as coagulation exclusively targeted oxidized organic matter components while NF removed both chemically reduced and oxidized components. DOC removal and change in DOC character in the GAC filters showed marked differences with slower saturation and more pronounced shifts in DOC character using NF as pre-treatment. Fluorescence derived parameters showed a similar decrease over time of GAC performance for the first 150 days but also indicated ongoing change of DOM character in the post NF GAC filtrate over time even after LC-OCD indicated steady state with respect to outgoing carbon. During our trial iron concentrations were low (<30 ppb) and thus A254 could be directly related to the concentration of HS (R(2) = 0.9). The fluorescence derived freshness index (β:α) proved to be an excellent variable for estimating the fraction of HS present in all samples. Given the recommended limit of 4 mg L(-1) for chemical oxygen demand (COD) for Swedish drinking water, coagulation will need to be supplemented with one or more treatment steps irrespective whether climate change will lead to drier or wetter conditions in order to maintain sufficient DOC removal with the current increasing concentrations in raw waters.
北欧国家地表水中有机物浓度不断上升,要求当前的饮用水处理工艺进行相应调整。因此,在瑞典斯德哥尔摩的一个大型饮用水处理厂,采用新型纳滤(NF)膜进行了为期九个月的中试研究。在该中试研究中,采用耐化学腐蚀性的中空纤维 NF 膜,以硫酸铝混凝后的快滤池出水为进水进行处理。混凝和 NF 联合工艺去除了超过 90%的入湖水中溶解性有机碳(DOC)(8.7 mg C L(-1))和 96%的 254nm 吸光度(A254)(0.28 cm(-1) 进水吸光度)。包括颗粒活性炭(GAC)过滤器在内,我们观察到完整的中试处理工艺可降低 DOC 浓度(8.7-0.5 mg C L(-1))、SUVA(3.1-1.7 mg(-1) L m(-1))和平均标称分子量(670-440 Da)。同时,水硬度基本不受影响(<20%的降幅)。腐殖质(HS)和生物聚合物几乎完全去除(分别为 6510-140 和 260-10μg C L(-1)),且低分子量(LMW)中性物质大量减少(880-190μg C L(-1))。微分激发发射矩阵(EEM)说明了在一系列激发和发射波长范围内可去除荧光有机物(FDOM),表明混凝可去除 35±2%的蛋白样物质和 65±2%的长发射波长、类腐殖质 FDOM。随后的 NF 处理的选择性稍差,但仍优先针对类腐殖质 FDOM(83±1%),而不是蛋白样物质(66±3%)。傅里叶变换离子回旋共振质谱(FT-ICR-MS)和带有有机碳检测的液相色谱(LC-OCD)分析证实,与 NF 分离相比,混凝对有机物的选择性更高,因为混凝专门针对氧化的有机物质成分,而 NF 则去除了化学还原和氧化的成分。GAC 过滤器中的 DOC 去除和 DOC 特征的变化表明,使用 NF 作为预处理时,GAC 的饱和速度较慢,DOC 特征的变化更为明显。荧光衍生参数在 GAC 运行的前 150 天内也显示出类似的下降,但也表明即使 LC-OCD 表明出碳输出达到稳定状态,NF 后 GAC 滤出液中的 DOM 特征仍在不断变化。在我们的试验中,铁浓度较低(<30 ppb),因此 A254 可直接与 HS 浓度相关(R(2) = 0.9)。荧光衍生的新鲜度指数(β:α)被证明是一个很好的变量,可以估计所有样品中 HS 的含量。鉴于瑞典饮用水中化学需氧量(COD)的建议限值为 4 mg L(-1),无论气候变化导致水源中有机物浓度增加是使情况变得更干燥还是更湿润,为了保持足够的 DOC 去除率,都需要添加一个或多个处理步骤来补充混凝工艺。