水中痕量多环芳烃类物质的分析检测及纳滤去除特性研究
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摘要
多环芳烃(PAHs)类物质在环境中存在广泛,由于其毒性、生物蓄积性和半挥发性使其在环境中持久存在,故被列入典型持久性有机污染物(POPs),受到了人们的广泛关注。本文以萘、菲、荧蒽为研究对象,研究改进PAHs类物质的浓缩和检测方法,并通过小型错流膜过滤装置研究不同操作压力、pH值、离子强度条件下纳滤膜对PAHs类物质的去除特性。
通过试验研究,得出以下结果:
(1)样品前处理的最佳固相萃取条件为:上样流速5mL/min,二氯甲烷洗脱,洗脱剂用量3mL,洗脱流速2mL/min。采用气相色谱-质谱联用(GC/MS)对水中痕量PAHs进行了测定,方法检出限为0.03～0.07μg/L,加标回收率为70～96%,相对标准偏差为3.90～9.58%。测定结果显示,该方法相关性好、精度高,能满足水中痕量PAHs的测定要求。
(2)分别采用纯水和添加了腐殖酸的溶液与PAHs标准物质配制成一定浓度PAHs水样,研究纳滤在这两种水质条件下对PAHs的去除特性。研究发现下列因素影响纳滤膜对PAHs的截留效果:
①在纯水条件下比以腐殖酸为主的可溶性有机质共存条件下的膜通量大,截留率小。说明腐殖酸类物质对提高纳滤膜截留PAHs类物质有改善作用,但在该条件下纳滤膜的制水量较低。
②在纯水条件下,操作压力与膜通量成正比,与截留率成反比;原水浓度与膜通量成反比,与截留率也成反比;pH和离子强度条件的改变会影响膜结构和膜面分子作用力。低pH值或高离子强度下,由于膜面分子双电层被压缩,膜面对PAHs分子的斥力减小,因而PAHs分子易吸附在膜面上,膜通量较低,截留率较大。在高pH值或低离子强度下,膜孔扩大,PAHs不易吸附在膜面上,膜通量较大,截留率较小。
③在以腐殖酸为主的可溶性有机质共存条件下,pH值增大时,腐殖酸中更多的羧基官能团质子化,使得膜面分子之间、膜面分子和溶液中PAHs分子之间的斥力减小,因而膜通量随之增大。Ca~(2+)能够与腐殖酸中的酸性官能团形成络合物,且由于络合作用腐殖酸的链与链之间的静电斥力减小,使其形成盘绕状的腐殖质大分子。随着Ca~(2+)浓度增加,膜表面污染层的密实程度加剧,导致膜通量减小,PAHs的截留率增加。
④纳滤膜对PAHs类物质的吸附试验表明,大约经历6h吸附即会达到平衡,此后纳滤膜对PAHs物质的去除主要靠筛分作用完成。
⑤BDXN-90比BDXN-70去除PAHs的截留率高。BDXN-90去除率在99%以上,但产水率较低,但是可以通过改变pH值和离子强度等来优化过滤条件。试验证明BDXN-90分离PAHs的效果是稳定的,可以推广至实际应用。
Polycyclic aromatic hydrocarbons(PAHs) exist in the environment widely, because of their toxicity,bioaccumulation and semi-volatile and persistent in the environment,and included in a typical persistent organic pollutants(POPs),were attentioned widely by the scientific community.In this paper,naphthalene, phenanthrene,fluoranthene as the studied objects,the concentration and analytical methods were investigated and improved.Then the effects of test parameters such as operation pressure,pH,ionic strength on the character of removing PAHs by nanofiltration membrane(NF) filtration process were investigated.The main conclusions are as follows:
(1) With orthogonal experiment,the optimal SPE conditions obtained were 5mL/min for sampling flow rate,3mL of dichloromethane for elution volume,2mL/min for elution flow rate.The results showed the detection limit of the method was 0.03～0.07μg/L,the recovery efficiency was in a range of 70%～96%and the relative standard deviations was in a range of 3.90%～9.58%.The method had better linear relativity and high precision,which could satisfy the requirements to determine the trace PAHs concentration in water.
(2) The characteristic of PAHs removed by nanofiltration membrane(NF) filtration process was investigated with two process as follows:pure water and water(humic acid added) as solvent,then mixed with PAHs.The following factors influence the removal rate.
①The membrane permeability under pure water conditions was higher than the humic acid coexistence,but the removal rate was opposite.This shows that the humic acid in surface water could improve the removal rate of PAHs,but the water preparation amount was lower under this condition.
②The operation pressure was proportional to membrane flux,and removal rate was inversely proportional to the operation pressure;the concentration of raw water was inversely proportional to the membrane flux and the removal rate.pH and ionic strength would change the membrane structure and membrane surface intermolecular forces.At low pH or high ionic strength,electric double layer of the membrane surface molecular were compressed,while the repulsive forces between membrane surface and PAHs decrease,leading to that the PAHs molecules adsorbed on the membrane surface easily, low membrane flux,and high removal rate.Under high pH and low ion strength,the result was opposite.
③Under the condition of humic acid coexistence,carboxyl functional groups from the humic acid material were protonated as the pH increasing.It leaded to repulsive forces decreasing among membrane surface molecules and the force between the membrane surface molecules and PAHs.As a result,the membrane flux increased. Complex would be formed by Ca~(2+) and acidic functional groups from humic acid material.The electrostatic repulsion among the humic acid material's chain reduced for comlex formed,which leaded to the formation of coiling-shape huge humic molecules. With the Ca~(2+) concentration increasing,dense degree of membrane surface contamination layer was increasing.It leaded to the lower membrane flux and higher removal rate.
④The adsorption tests of nanofiltration to PAHs showed that the adsorption equilibrium were finished after 6h,after this the PAHs removal through nanofiltration were accomplished with screening.
⑤The removal rate of BDXN-90 were higher than BDXN-70.The removal rate of BDXN-90 was all above 99%.BDXN-90 has lower water preparation amount,but the filtration condition could be optimized by changing pH and ionic strength.It testified that BDXN-90 has stable separation of PAHs and can be extended to practical applications.
通过试验研究,得出以下结果:
(1)样品前处理的最佳固相萃取条件为:上样流速5mL/min,二氯甲烷洗脱,洗脱剂用量3mL,洗脱流速2mL/min。采用气相色谱-质谱联用(GC/MS)对水中痕量PAHs进行了测定,方法检出限为0.03～0.07μg/L,加标回收率为70～96%,相对标准偏差为3.90～9.58%。测定结果显示,该方法相关性好、精度高,能满足水中痕量PAHs的测定要求。
(2)分别采用纯水和添加了腐殖酸的溶液与PAHs标准物质配制成一定浓度PAHs水样,研究纳滤在这两种水质条件下对PAHs的去除特性。研究发现下列因素影响纳滤膜对PAHs的截留效果:
①在纯水条件下比以腐殖酸为主的可溶性有机质共存条件下的膜通量大,截留率小。说明腐殖酸类物质对提高纳滤膜截留PAHs类物质有改善作用,但在该条件下纳滤膜的制水量较低。
②在纯水条件下,操作压力与膜通量成正比,与截留率成反比;原水浓度与膜通量成反比,与截留率也成反比;pH和离子强度条件的改变会影响膜结构和膜面分子作用力。低pH值或高离子强度下,由于膜面分子双电层被压缩,膜面对PAHs分子的斥力减小,因而PAHs分子易吸附在膜面上,膜通量较低,截留率较大。在高pH值或低离子强度下,膜孔扩大,PAHs不易吸附在膜面上,膜通量较大,截留率较小。
③在以腐殖酸为主的可溶性有机质共存条件下,pH值增大时,腐殖酸中更多的羧基官能团质子化,使得膜面分子之间、膜面分子和溶液中PAHs分子之间的斥力减小,因而膜通量随之增大。Ca~(2+)能够与腐殖酸中的酸性官能团形成络合物,且由于络合作用腐殖酸的链与链之间的静电斥力减小,使其形成盘绕状的腐殖质大分子。随着Ca~(2+)浓度增加,膜表面污染层的密实程度加剧,导致膜通量减小,PAHs的截留率增加。
④纳滤膜对PAHs类物质的吸附试验表明,大约经历6h吸附即会达到平衡,此后纳滤膜对PAHs物质的去除主要靠筛分作用完成。
⑤BDXN-90比BDXN-70去除PAHs的截留率高。BDXN-90去除率在99%以上,但产水率较低,但是可以通过改变pH值和离子强度等来优化过滤条件。试验证明BDXN-90分离PAHs的效果是稳定的,可以推广至实际应用。
Polycyclic aromatic hydrocarbons(PAHs) exist in the environment widely, because of their toxicity,bioaccumulation and semi-volatile and persistent in the environment,and included in a typical persistent organic pollutants(POPs),were attentioned widely by the scientific community.In this paper,naphthalene, phenanthrene,fluoranthene as the studied objects,the concentration and analytical methods were investigated and improved.Then the effects of test parameters such as operation pressure,pH,ionic strength on the character of removing PAHs by nanofiltration membrane(NF) filtration process were investigated.The main conclusions are as follows:
(1) With orthogonal experiment,the optimal SPE conditions obtained were 5mL/min for sampling flow rate,3mL of dichloromethane for elution volume,2mL/min for elution flow rate.The results showed the detection limit of the method was 0.03～0.07μg/L,the recovery efficiency was in a range of 70%～96%and the relative standard deviations was in a range of 3.90%～9.58%.The method had better linear relativity and high precision,which could satisfy the requirements to determine the trace PAHs concentration in water.
(2) The characteristic of PAHs removed by nanofiltration membrane(NF) filtration process was investigated with two process as follows:pure water and water(humic acid added) as solvent,then mixed with PAHs.The following factors influence the removal rate.
①The membrane permeability under pure water conditions was higher than the humic acid coexistence,but the removal rate was opposite.This shows that the humic acid in surface water could improve the removal rate of PAHs,but the water preparation amount was lower under this condition.
②The operation pressure was proportional to membrane flux,and removal rate was inversely proportional to the operation pressure;the concentration of raw water was inversely proportional to the membrane flux and the removal rate.pH and ionic strength would change the membrane structure and membrane surface intermolecular forces.At low pH or high ionic strength,electric double layer of the membrane surface molecular were compressed,while the repulsive forces between membrane surface and PAHs decrease,leading to that the PAHs molecules adsorbed on the membrane surface easily, low membrane flux,and high removal rate.Under high pH and low ion strength,the result was opposite.
③Under the condition of humic acid coexistence,carboxyl functional groups from the humic acid material were protonated as the pH increasing.It leaded to repulsive forces decreasing among membrane surface molecules and the force between the membrane surface molecules and PAHs.As a result,the membrane flux increased. Complex would be formed by Ca~(2+) and acidic functional groups from humic acid material.The electrostatic repulsion among the humic acid material's chain reduced for comlex formed,which leaded to the formation of coiling-shape huge humic molecules. With the Ca~(2+) concentration increasing,dense degree of membrane surface contamination layer was increasing.It leaded to the lower membrane flux and higher removal rate.
④The adsorption tests of nanofiltration to PAHs showed that the adsorption equilibrium were finished after 6h,after this the PAHs removal through nanofiltration were accomplished with screening.
⑤The removal rate of BDXN-90 were higher than BDXN-70.The removal rate of BDXN-90 was all above 99%.BDXN-90 has lower water preparation amount,but the filtration condition could be optimized by changing pH and ionic strength.It testified that BDXN-90 has stable separation of PAHs and can be extended to practical applications.
引文
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