Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents

Removal of polycyclic aromatic hydrocarbons （PAHs）, e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorpfion kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains （i.e., exposed aromatic core）. By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorpfion coefficients （Kd） were negatively correlated with the polarity index [（O＋N）/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater.     

深圳湾生态系统多环芳烃(PAHs)特征及其生态危害

2004年在深圳湾海域采集海水、悬浮物、表层沉积物和柱状沉积物样品,并分析其中15种多环芳烃的含量及其相关参数,同时采用210Pb法测定柱状沉积物的年龄.结果表明,海水、悬浮物、表层沉积物和柱状沉积物中总的PAHs含量分别为(69.4±24.7)ng·L-1、(429.1±231.8)ng·g-1、(353.8±128.1)ng·g-1和(321.1±134.6)ng·g-1,各介质优势组分均为菲、荧蒽和芘;1948～2004年期间,深圳湾柱状沉积物中PAH各单体的浓度总体上一直在增加,PAHs的平均沉积通量为89.9ng/(cm2·a);PAH各单体在沉积物/海水中的分配系数(Koc)与其相应的辛醇/水比(Kow)存在明显的正相关性,即可用PAH的Kow值来预测深圳湾海域PAH的Koc.目前,水体与沉积物中PAH含量对该海域的水生生物尚未构成威胁.     

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene (m-DNB) and nitrobenzene to original bentonite in aqueous solution containing di erent electrolytes (i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide (TMAB)) was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl > NH4Cl TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out e ect is insu cient to account for the sorption enhancement by original bentonite with increasing KCl or NH4Cl concentration. X-ray di raction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K+ or NH4 + into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K+ at high solute-loadings (> 200–400 mg/kg). The sorption of m-DNB to initially modified TMA+-bentonite and K+-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA+ and K+.     

多环芳烃在长江口滨岸颗粒物-水相间的分配

利用长江口滨岸水环境中颗粒相与溶解相多环芳烃的实测浓度,获取了多环芳烃化合物在颗粒物-水相间的分配系数K_p.结果表明,分配系数K_p值在507～10 179 L/kg之间,枯季高于洪季,随多环芳烃环数的增加而增大;K_oc值与辛醇-水分配系数K_ow之间存在较好的线性自由能关系（枯季R²＝0.82,洪季R²＝0.68）,推断出长江口滨岸颗粒物亲脂性较差,对多环芳烃的吸收能力相对较弱.长江口滨岸各采样点多环芳烃化合物的lgK_oc值均超过了经典平衡分配模型的预测值上限,多环芳烃两相分配行为不受颗粒物浓度、粒径及上覆水盐度、溶解态有机碳的控制（R²<0.1）,表现出主要受POC及非均一性混合物PSC共同影响的特点;扩展后的含PSC相的颗粒物-水相分配模型较为准确地模拟了lgK_ow<6的多环芳烃化合物野外原位分配过程.     

水溶性有机碳对菲吸附系数测定的影响

以菲为代表性化合物,利用摇瓶吸附实验研究土壤水分配体系中溶解态有机碳(DOC)对有机碳归一化吸附系数测定结果的影响.研究结果表明,在吸附系数测定过程中土壤溶出的DOC会导致水相中菲的浓度显著增加,很大程度上改变了菲在土水两相中的分配平衡,从而导致吸附系数的测定误差.根据文献报道的菲与DOC相互作用常数(K_doc)以及实测体系中DOC浓度可以对实验数据进行校正,以获得更为可靠的结果,本文对线性吸附系数和Freundlich吸附系数分别进行了校正,得到有机碳归一化的吸附系数lgKoc为4.35 ,lgK_Foc为7.01.校正前后的lgK_oc与文献数据的对比从侧面反映出在水土体系的吸附研究中可能普遍包含因不同浓度DOC影响所造成的偏差,考虑这种影响对于准确比较不同研究得到的吸附参数具有重要意义.     

表面活性剂对极性有机物在沉积物上吸附的影响

研究了苯酚、苯胺和对硝基苯酚在沉积物-十二烷基苯磺酸钠(SDBS)体系中的分配特性.结果表明200mg/L和1200mg/L的SDBS存在下,苯胺和对硝基苯酚的沉积物-水分配系数均增大,分配作用的增大倍数与有机物的K_ow呈正相关;苯酚的分配系数则因表面活性剂存在浓度的不同分别增大和减小.十二烷基硫酸钠(SDS)、Triton X-100(TX100)和Brij30存在下,苯酚等温吸附实验表明:表面活性剂浓度约低于其临界胶束浓度(CMC)时,苯酚的吸附量增大;表面活性剂浓度约高于其CMC时,苯酚的吸附量比纯水中的吸附量小.     

珠江三角洲表层水中多环芳烃的季节分布、来源和原位分配

分别于2011年4月(春季)和2011年9月(夏季)采集珠江广州河段及东江东莞河段表层水体样品,对该区域表层水体中优控多环芳烃(PAHs)的时空分布、固液分配及其来源进行了分析和讨论.结果表明,珠江广州河段及东江东莞河段表层水体中多环芳烃浓度春季高于夏季.藻类有机碳是该水环境有机碳的主要成分.溶解有机碳(DOC)、颗粒态有机碳(POC)以及叶绿素a(Chl a)含量是控制水体PAHs浓度的主要因素,说明水环境的富营养化程度可以通过增长的浮游生物量来影响多环芳烃的生物地球化学过程,继而影响其环境行为和归宿.多环芳烃在水/颗粒物间的有机碳归一化分配系数(log Koc)与辛醇/水分配系数(log Kow)间存在明显的线性关系,其斜率是夏季大于春季,可能与多环芳烃的非平衡吸附有关.多环芳烃同系物比值法和主成分分析(PCA)的结果表明,研究区域水体中PAHs主要来源于石化燃料、煤和生物质的混合燃烧,并且PAHs的来源未体现出明显的季节变化.通过本研究我们能够比较全面的了解该流域多环芳烃的时空分布状况,固液分配及其可能的来源,并且为珠江广州河段及东江东莞河段多环芳烃污染的控制和生态风险评价提供科学依据.     

不同来源土样胶体对氯霉素吸附行为的影响

选取不同来源沉积物或土壤样品（沉积物A1和A2,天然土壤B1和B2,市售营养土B3）,采用切向超滤与多种纳米分析技术相结合的方法,分析了不同土样中胶体的理化特征及其对氯霉素（CAP）吸附行为的影响.荧光区域积分法结果显示,土样胶体的荧光组分以色氨酸类蛋白质、类富里酸和类腐殖酸为主,络氨酸类蛋白质和溶解性微生物代谢物质存在较少.吸附实验结果表明,B3胶体对CAP的吸附率最大（36.25%）,在胶体浓缩液和超滤液中的分配比例最高（1.91）,但其有机碳归一化结合系数最低（3.93）.与天然土壤相比,河湖沉积物胶体的吸附率较高,但其与CAP的结合能力却较低.冗余分析结果表明,胶体对CAP的吸附主要与其芳香度、有色溶解性有机质丰度、溶解性有机碳浓度及分子量有关;此外,胶体的腐殖化程度、芳环上羧基、羰基等官能团的比重及荧光物质中溶解性微生物代谢产物和类腐殖酸对CAP的吸附行为也具有较大影响.     

Removal of polycyclic aromatic hydrocarbons and phenols from coking wastewater by simultaneously synthesized organobentonite in a one-step process

The optimal condition for a one-step process removing organic compounds from coking wastewater by simultaneously synthesized organobentonite as a pretreatment was investigated. Results showed that sorption of organic compounds by organobentonite was positively correlated to the cation surfactant exchange on the bentonite and the octanol-water partition coefficient (K_ow) of the solutes. With 0.75 g/L bentonite and 180 mg/L (60% of bentonite cation exchange capacity) cetyltrimethylammonium bromide, the removal efficiencies of the 16 polycyclic aromatic hydrocarbon (PAHs) specified by the US Environmental Protection Agency in coking wastewater except naphthalene were more than 90%, and that of benzo(a)pyrene was 99.5%. At the same time, the removal efficiencies of COD_Cr, NH₃-N, volatile phenols, colour and turbidity were 28.6%, 13.2%, 8.9%, 55% and 84.3%, respectively, and the ratio of BOD₅/COD_Cr increased from 0.31 to 0.41. These results indicated that the one-step process had high removal efficiency for toxic and refractory hydrophobic organic compounds, and could improve the biodegradability of the coking wastewater. Therefore it could be a promising technology for the pretreatment of toxic and refractory organic wastewater.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r ² = 0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK _FOC values of 6.02 to 6.42 (μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C _e, the BC had higher K _oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C _e= 0.05 S _w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

卤代苯化合物水溶解度及正辛醇/水分配系数的三维构效关系研究

对卤代苯化合物的水溶解度(-lg Sw)和正辛醇/水分配系数(lg Kow)分别进行了基于三维结构的比较分子场(Co MFA)和比较分子相似性指数(Co MSIA)分析,建立了三维定量结构-性质相关(3D-QSPR)模型,并将所获结果与密度泛函理论(DFT)方法得到的2D-QSPR模型进行了比较.结果表明:-lg Sw的Co MFA和Co MSIA模型交叉验证相关系数Q2分别为0.902和0.940,决定系数R2分别为0.982和0.986,模型稳定性和估算能力较好;lg Kow的Co MFA和Co MSIA模型Q2分别为0.926和0.988,R2分别为0.983和0.997;本研究所建的3D-QSPR模型的估算能力优于2D-QSPR模型;Co MFA和Co MSIA模型三维等势图表明,取代基的疏水效应对该类化合物的水溶解性能及正辛醇/水分配系数的影响更为显著,立体效应次之,静电场效应影响较小.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Effect of biosurfactant on the sorption of phenanthrene onto original and H2O2-treated soils

The objective of this study was to examine the effect of biosurfactant on the sorption of phenanthrene (PHE) onto the original or H2O2-treated black loamy soil (typic isohumisols) and red sandy soil (typic ferralisols). The sorption isotherms were performed with the original and “soft” carbon-removed soils in the presence and absence of biosurfactant (200 mg/L). The sorption and degradation of biosurfactant were investigated. The result showed that organic matter played an important role in PHE sorption onto the black loamy and red sandy soils, and the PHE sorption isotherms on the “soft” carbon-removed soils exhibited more nonlinearity than those on the original soils. The values of partition coe cient (Kd) on the original black loamy soil with or without 200 mg/L biosurfactant were 181.6 and 494.5 mL/g, respectively. Correspondingly, in the red sandy soil, Kd was 246.4 and 212.8 mL/g in the presence or absence of biosurfactant, respectively. The changes of Kd suggested that biosurfactant inhibited PHE sorption onto the black loamy soil, but facilitated PHE sorption onto the red sandy soil. The nonlinearity of PHE sorption isotherm was decreased in the presence of biosurfactant. Site specific sorption might occur during PHE sorption onto both the original and the “soft” carbon-removed soils in the presence of biosurfactant. It was noted that biosurfactant could also be sorbed onto soils. The maximal sorption capacity of the red sandy soil for biosurfactant was (76.9 0.007) g/g, which was 1.31 times that of black loamy soil. Biosurfactant was degraded quickly in the two selected soils, and 92% of biosurfactant were mineralized throughout the incubation experiment for 7 d. It implied that biosurfactant should be added frequently when the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils was conducted through PAH desorption approach facilitated by biosurfactant.     

Sorption and phase distribution of ethanol and butanol blended gasoline vapours in the vadose zone after release

The sorption and phase distribution of 20% ethanol and butanol blended gasoline （E20 and B20） vapours have been examined in soils with varying soil organic matter （SOM） and water contents via laboratory microcosm experiments. The presence of 20% alcohol reduced the sorption of gasoline compounds by soil as well as the mass distribution of the compounds to soil solids. This effect was greater for ethanol than butanol. Compared with the sorption coefficient （Kd） of unblended gasoline compounds, the Kd of E20 gasoline compounds decreased by 54% for pentane, 54% for methylcyclopentane （MCP） and 63% for benzene, while the Kd of B20 gasoline compounds decreased by 39% for pentane, 38% for MCP and 49% for benzene, The retardation factor （R） of E20 gasoline compounds decreased by 53% for pentane, 53% for MCP and 48% for benzene, while the R of B20 gasoline compounds decreased by 39% for pentane, 37% for MCP and 38% for benzene. For all SOM and water contents tested, the Kd and R of all gasoline compounds were in the order of unblended gasoline 〉 B20 〉 E20, indicating that the use of high ethanol volume in gasoline to combat climate change could put the groundwater at greater risk of contamination,     

农药微生物降解性与农药疏水性参数间的相关性

在纯培养条件下，产碱菌属广说性降解菌ＹＦ１１对对硫磷，甲基对硫磷，杀螟松，氰戊菊酯，溴氰菊酯，甲氰菊酯，氯氰菊酯，三氟氯氰菊酯，氯菊酯的降解速率的差异主要是由各杀虫剂的疏水性参数的不同引起的，两之间存在较好的相关性：ｌｏｇＫ＝２．２１－０．２６ｌｏｇＫｏｗ，ｒ＝０．９７３９。     

改性土壤对模拟含油废水中油的吸附

研究季铵盐阳离子表面活性剂四甲基铵离子 ( TMA)和十六烷基三甲基铵离子 ( HDTMA)改性的土壤 (黑土、黄棕壤、红壤 )对水中油的吸附作用 .结果表明 :改性土壤和未改性土壤均可吸附水中的油 ,但改性土壤对水中油的吸附能力明显高于未改性土壤 .改性土壤吸附油能力的顺序依次为 :1 CEC- HDTMA黑土 >1 CEC-HDTMA黄棕壤 >1 CEC- HDTMA红壤 >1 CEC-TMA黑土 >1 CEC-TMA黄棕壤 >1 CEC- TMA红壤 .未改性土壤和 HDTMA改性土壤对油的吸附通过分配来进行 ,吸附等温线可由 Henry方程表示 ,得出 logK_SOM为 2.69,logK_HDTMA为 3.35;TMA改性土壤对油的吸附符合 Langmuir方程 ,其对油的饱和吸附量分别为 1150 mg/kg( TMA黑土 ) ,751 mg/kg( TMA黄棕壤 ) ,172 mg/kg( TMA红壤 )     

取代联苯的定量结构活性相关及联合毒性研究

测定了18种取代联苯对大型蚤(Daphnia magna)24h的单一毒性(24h-EC₅₀)及其混合物联合毒性.对单一毒性进行了定量结构活性相关(QSAR)分析,建立了辛醇-水分配系数(lgK_ow)模型,理论线性溶剂化能相关(TLSER)模型及量子化学参数模型,表明量子化学参数模型能很好地预测取代联苯的单一毒性.混合物联合毒性研究表明,取代联苯的联合毒性机制为浓度相加效应,并且根据浓度相加预测了混合物半数抑制浓度(EC_50mix),预测值与实验值非常吻合.     

表面活性剂改性沸石对水中酚类化合物吸附性能研究

使用表面活性剂对2种粉煤灰合成沸石进行改性处理,研究改性沸石对酚类化合物（苯酚、对氯酚和双酚A）的吸附特性.吸附试验结果表明,合成沸石经过阳离子表面活性剂十六烷基三甲基溴化铵改性后,对酚类化合物的吸附性能均有大幅提升,吸附等温线模型均较符合Langmuir模型.2种改性沸石对酚类化合物（苯酚、对氯酚和双酚A）的Langmuir理论最大吸附量分别可达37.7、52.36、90.9 mg.g-1和10.71、22.83、56.8 mg.g-1.当溶液pH值高于酚类化合物的解离系数pKa时,吸附效果随pH升高而增加.结果还表明,酚类化合物的疏水性（辛醇/水分配系数Kow）越强,改性沸石的吸附能力也越高.     

卤系阻燃剂在东江工业水体中的质量浓度及其分配特征

本研究分析了东江工业水体中卤系阻燃剂的浓度,组成分布以及分配特征.结果表明多溴联苯醚(PBDEs)是水体中的主要的卤系阻燃剂,占总卤系阻燃剂的41.0%,其质量浓度范围为1 102.3~3 666.9 pg·L~(-1),其中BDE209是颗粒相的主要成分.四溴双酚A(TBBPA)占总卤系阻燃剂的32.4%,其质量浓度范围为1 120.9~2 856.5 pg·L~(-1),其他卤系阻燃剂如十溴二苯乙烷(DBDPE)、德克隆(DP)和六溴环十二烷(HBCDs)分别占总卤系阻燃剂的16.3%、7.3%和3.0%,其质量浓度范围分别为397.7~1 736.8、235.7~778.1和9.5~266.8 pg·L~(-1).在对水体溶解相和颗粒相分配的研究中发现,PBDEs、DBDPE、DP和HBCDs主要存在于水体颗粒相中,而TBBPA由于其较大的水溶性,主要存在于溶解相中;卤系阻燃剂的lgK_(oc)与lgK_(ow)之间存在显著的相关性,但是lgK_(oc)实测值与其理论预测值有一定差异,这可能是受控于悬浮颗粒(SPM)含量和溶解有机碳(DOC)含量这两个因素,此外,颗粒相和溶解相之间分配是否达到平衡也是影响测量lg Koc值的因素.     

固相微萃取模拟生物法用于养殖底泥多环芳烃污染监测的研究

本研究以养殖底泥中多环芳烃(PAHs)为研究对象,采用以聚二甲基硅氧烷(PDMS)为材料测定孔隙水中PAHs自由溶解态浓度(Cfree)的固相微萃取技术,以重要海水经济底栖生物菲律宾蛤仔(Ruditapes philippinarum)为参照生物,建立了PDMS中PAHs浓度与菲律宾蛤仔脂肪标化及底泥有机碳标化的PAHs浓度间的定量关系模型,进一步证明了基于固相微萃取的模拟生物法用于养殖区域中多环芳烃监测的可能性.结果表明,孔隙水中自由溶解态PAHs浓度(Cfree)显著低于孔隙水中总PAHs浓度(Cwater),且随着环数增加,两者间的差异越大,说明Cwater忽视了生物有效性,从而会高估孔隙水中PAHs的环境风险,因此,Cfree能更好地反映底泥孔隙水中PAHs的暴露水平;菲律宾蛤仔对PAHs的富集系数(BAF)及PDMS-水分配系数(KPDMS)均与辛醇-水分配系数(Kow)呈显著线性相关,且两者斜率相近,说明菲律宾蛤仔摄取PAHs的主要途径与PDMS相似,且PDMS中PAHs的浓度与生物体内PAHs的残留浓度和底泥有机碳标化的PAHs浓度间均呈现显著相关,说明当底泥孔隙水中和PDMS膜之间达到平衡时,固相微萃取模拟生物法可以用于计算底栖生物和沉积物中有机污染物,具有应用于养殖区域中多环芳烃监测的潜力,但有机污染物在生物体内转化和底泥性质对相关关系和监测应用的影响有待进一步研究.