广西百朗地下河水和沉积物中有机氯农药的分布特征

为了解典型岩溶地区广西乐业百朗地下河表层水和沉积物中有机氯农药的分布特征,采集地下河不同断面的水和沉积物样品,利用气相色谱仪测定了19种有机氯农药。结果表明:(1)百朗地下河表层水中19种有机氯农药总量(∑OCPs)浓度为1.95～71.45ng/L,HCHs和DDTs浓度分别为未检出至58.40ng/L和未检出至0.44ng/L;(2)沉积物中∑OCPs浓度为0.75～14.85ng/g,HCHs和DDTs浓度分别为0.11～3.52ng/g和0.03～2.90ng/g;(3)地下河表层水和沉积物中有机氯农药的分布与吸附作用、环境温度以及和地下河连通的天坑的底部的土壤侵蚀有关,即因温差作用,大气沉降的有机氯农药易富集在天坑底部(“冷陷阱效应”),并在土壤侵蚀作用下向水体移动,使地下河沉积物中有机氯农药浓度升高;(4)百朗地下河出口沉积物吸附系数最低,但水中有机氯农药浓度较高且种类最多,推测可能是地下河沉积物中因有机氯农药被释放而引起二次污染;(5)表层沉积物中大多数断面的异狄氏剂浓度及乐业县城附近断面的DDTs和DDD浓度在风险评估低值与风险评估中值之间,表明百朗地下河处于较低的生态风险水平;(6)目前,流域部分断面尚有新的γ-HCH(林丹)和DDTs农药输入。由于有机氯农药长期累积,可能对地下河生态系统造成危害,应采取防治措施。      

柳州岩溶地下河水体有机氯农药分布特征

采用气相色谱(配ECD检测器)对柳州鸡喇和龙寨两条岩溶地下河不同位置水体中18种有机氯农药(OCPs)组分进行分析。结果表明,除异狄氏剂醛外,其余17种OCPs均有不同程度检出,OCPs浓度变化范围为107.68～1101.55ng/L,均值为532.515ng/L。OCPs主要组分为:α-HCH、β-HCH、γ-HCH、δ-HCH、p,p'-DDE、o,p'-DDT、p,p'-DDD、p,p'-DDT、六氯苯、七氯、艾氏剂。其中DDTs和HCHs含量最高,二者之和占到总OCPs的75.8%～96%。对其污染源进行分析,发现地下河水体中DDTs主要源自土壤。HCHs来源相对复杂,可能源于工业品或者长距离大气运输,也可能是近期有林丹的输入使其浓度增高。与国内外各水体相比,本次研究的两条岩溶地下河有机氯农药含量相对较高。      

表层岩溶带土壤中有机氯农药的分布及来源特征研究——以重庆南川区为例

为了研究有机氯农药(OCPs)在表层岩溶带土壤中的分布趋势、组成特征和来源,采用气相色谱-微池电子捕获检测器(GC-μECD)分析了重庆市南川区水房泉、后沟泉、柏树湾泉、兰花沟泉等典型表层带岩溶泉上覆土层中有机氯农药的浓度。结果显示,总体上表层岩溶带土壤中的OCPs的浓度范围是7.13~323.37ng/g,其中后沟泉、柏树湾泉、兰花沟泉表层土壤中的17种OCPs检出率为100%,水房泉土壤中除p,p'-DDD外其余全部检出,但不同种类有机氯含量差异较大。其中HCHs、DDTs、CHLs、灭蚁灵是主要检出物。研究区内土壤样品中的HCHs来源于工业品HCHs和林丹使用的残留,且由于环境影响,土壤中HCH的同系物组成发生了明显变化。水房泉和柏树湾泉土壤中的DDTs来自于工业DDTs和三氯杀螨醇的混合源,而后沟泉和兰花沟泉土壤中的DDTs可能来自于工业DDTs的使用,而非三氯杀螨醇类型的DDT。对比中国和荷兰的土壤质量标准,柏树湾泉土壤中DDTs浓度接近于荷兰无污染土壤的参考值,兰花沟泉土壤中的DDTs应属于轻度污染,后沟泉土壤中的DDTs和氯丹类化合物污染程度较重,而水房泉土壤为无污染土壤。      

有机改性硅藻土对甲基橙、酸性绿两种阴离子的吸附实验研究

阳离子表面活性剂十六烷基三甲基溴化铵可以有效对天然硅藻土进行有机改性,获得有机改性硅藻土。有机改性硅藻土对富含甲基橙、酸性绿溶液的吸附实验研究结果表明,在相同条件下,改性硅藻土对甲基橙的吸附效果比较好,对酸性绿的吸附效果不是很理想,但也远远高于硅藻土原土对这两种阴离子的吸附效果。在室温条件下,当甲基橙溶液的浓度为20mg/L时,改性硅藻土投加量为0.2g、pH值为4、吸附时间为80min,改性硅藻土对其的吸附效果较好;在室温条件下,当染料酸性绿溶液的浓度为20mg/L时,改性硅藻土投加量为0.15g、pH值为4、吸附时间为80min,改性硅藻土对其的吸附效果较好;两种阴离子的吸附过程均符合Freundlich模型。基于n值对比分析,改性硅藻土对甲基橙的吸附属于优惠吸附,而对酸性绿的吸附属于非优惠吸附。     

山东烟台地区苹果果园土壤中DDTs和HCHs残留分布特征与来源解析

为研究不同土壤类型中有机氯农药的残留特征、降解程度和来源途径,采集了山东烟台9个不同地质单元苹果园根系土壤和剖面土壤样品,用电子捕获检测器气相色谱法测定其中的滴滴涕(DDTs)和六六六(HCHs)。结果表明,研究区所有类型根系土壤中DDTs和HCHs均未超出《土壤环境质量标准》的二级土壤限值(500 ng/g);土壤中DDTs的残留量及检出率均高于HCHs,DDTs检出率为100%,平均残留量为71.7ng/g,而HCHs的检出率为19.70%,平均残留量为7.9 ng/g;根系土壤中DDTs各异构体平均浓度依次为p,p’-DDT>p,p’-DDE>o,p’-DDT>p,p’-DDD,而HCHs大部分以α-HCH形式存在,部分以β-HCH、γ-HCH存在。不同类型土壤中有机氯农药残留分布特征明显不同:DDTs在棕壤土(臧家庄)中最高(145.5 ng/g),在中粗粒砂土(武宁)中最低(24.1 ng/g);而HCHs在细砂质壤土(蛇窝泊)中最高(27.9ng/g)。各剖面土壤DDTs均在<20 cm层位中残留最高。DDTs和HCHs来源解析表明:研究区土壤为好氧条件;麻砂棕壤(官道和桃村)、黏细壤土(牟平)、细砂质壤土(蛇窝泊)和棕壤土(臧家庄)近年来仍有新的DDTs输入;大部分根系土壤均未发现HCHs新来源,但麻砂棕壤(桃村)在HCHs禁用后可能仍存在林丹的使用。     

重庆老龙洞地下河流域水体有机氯农药污染及来源初步研究

为查明重庆老龙洞地下河流域有机氯农药的污染情况及其特征和来源,通过气相色谱-微池电子捕获检测器(GC-μ ECD)检测水体OCPs含量.结果表明研究区水样中受到了有机氯农药不同程度的污染.α-HCH是研究区水体HCHs主要成分,HCHs的残留主要来自于大气长距离传输.DDTs的主要成分各采样点不尽相同.DDTs的输入为历史上工业DDTs的使用且在水体中其主要以好氧转化为主.与国内外河流相比较,老龙洞地下河流域水体有机氯农药含量处于较高水平.     

废弃生产场地有机氯农药的残留与迁移特征

我国历史上曾生产和使用了大量的有机氯农药,现存的有机氯农药生产企业场地是污染高风险区.先前的报道多集中在场地内污染特征研究,较少关注场地周边有机氯农药污染及其环境风险性.为了解有机氯农药场地土壤污染水平及其对周边环境的影响,本文以重庆某废弃有机氯农药场地及其周边为研究区域,分析土壤中六六六(HCHs)、滴滴涕(DDTs)及其降解产物的含量水平,阐明场地内污染特征以及周边土壤的残留规律,评估场地内及周边土壤中有机氯农药污染的人体健康风险.结果表明,场地土壤中∑HCHs的含量水平为3.89 ～ 13385.78 ng/g,低于国内已报道的其他污染场地.∑DDTs的含量水平为22.74 ～ 11186.10 ng/g,与已报道的我国张家口、扬州等地生产场地污染水平相当,但低于邢台、太原和青岛等地农药厂生产场地污染水平.该生产场地土壤中有机氯农药污染的人体致癌风险值均高于可接受的范围,属于重污染区.场地周边400 m范围的土壤中HCHs和DDTs的含量水平虽整体上低于场地内,但污染水平也较高,HCHs污染和DDTs污染的总致癌风险均超过了儿童可接受的限值.随着与生产场地距离的增加,场地周边土壤HCHs和DDTs的含量水平呈幂函数下降的趋势,这同时又表明生产场地有机氯农药仅对场地周边一定范围内的环境产生较大污染.因此,对于生产场地污染不能仅仅关注场地内,还应充分考虑场地周边一定范围内的污染与环境风险性.     

大石围天坑群土壤中有机氯农药的分布与富集特征

选择典型的岩溶地区广西乐业大石围天坑群为研究区,采集不同岩溶地形的土壤,利用 GC-ECD 气相色谱仪测定六六六(HCHs)和滴滴涕(DDTs)两种有机氯农药的浓度.结果表明,大石围天坑群地表土壤、天坑绝壁土壤、天坑底部土壤以及地下河(洞穴)土壤中的 HCHs 和 DDTs 平均浓度分别为0.06 ng/g 和0.02 ng/g、0.31 ng/g 和0.27 ng/g、0.96 ng/g 和0.28 ng/g 以及0.14 ng/g 和0.10 ng/g.研究区土壤中有机氯农药总检出率为:天坑地表<天坑绝壁<天坑底部<地下河(洞穴),随高程降低而增高;有机氯农药(OCPs = HCHs + DDTs)浓度的空间分布特征为:天坑底部>天坑绝壁>地下河(洞穴)>天坑地表,天坑底部 OCPs 浓度明显高于顶部;因此,大石围天坑呈现明显的有机污染物“冷陷阱效应”     

长三角部分地区土壤中22种有机氯农药的分布特征

针对长三角地区长期工业化对农业生态环境构成较大风险,本文利用气相色谱法对该地区不同利用类型土壤中22种有机氯农药进行测定,研究了有机氯农药的残留状况及其在4条土壤垂向剖面中的分布特征。结果表明,不同利用类型表层土壤中有机氯农药残留平均值为工业园区菜地(139.87 ng/g)工业园区荒地(103.1 ng/g)农业区传统菜地(26.27 ng/g)农业区水稻田(2.50 ng/g)。表层土壤中DDTs和HCHs是主要污染物,DDTs含量为0.14~485.73 ng/g(均值44.43 ng/g),HCHs含量为0.69~66.69 ng/g(均值7.73 ng/g),(DDD+DDE)/DDTs值表明该地区近期外源DDTs输入较少。土壤剖面样品分析表明,DDTs和HCHs的含量均随土壤深度增加而迅速降低,这与剖面土壤包气带岩性均以黏土和亚黏土为主,削弱了地表径流对有机氯农药的垂直迁移动力有关。本研究可为控制和改善该地区污染状况提供相关数据。     

福建兴化湾水体有机氯农药污染状况

利用气相色谱-电子检测器对福建兴化湾河水和海水中的19种有机氯农药(HCHs、DDTs等)进行的分析结果表明,几种有机氯农药尽管已停止生产多年,但在河水及海水中仍有残留.二者的有机氯农药的质量浓度分别为10.96～56.31,5.78～161.64 ng/L ,同国内外其他港口海区及河流相比,其污染程度相对较低.丰水期河水中DDT的降解产物主要为DDE,而海水中DDT的降解产物主要为DDD.同时,对有机氯农药现状的分析表明,近年来仍有有机氯农药污染的输入,其农药的使用主要集中在六六六和滴滴涕上.     

利用多介质模型研究有机氯农药的环境行为

应用Ⅲ级多介质逸度环境模型研究了研究区3种有机氯农药p,p-’DDT、p,p-’DDE、p,p-’DDD的多介质行为。模型的计算结果表明:在研究区大气、水和沉积物中p,p-’DDT的浓度分别为0.019 8g/m3、0.016 8ng/L0、.313ng/g;p,p-’DDE的浓度分别为0.019 9g/m30、.001 65ng/L、0.124ng/g;p,p-’DDD的浓度分别为0.001 98g/m3、0.004 68ng/L、0.083 2ng/g。沉积物中的有机氯农药的含量占环境中有机氯农药总滞留量的99%以上,是有机氯农药的最主要的汇。然后计算了3种有机氯农药在环境中的相间迁移通量,其中水-沉积物迁移和沉积物-水迁移是最重要的迁移过程。     

微波萃取-气相色谱/气相色谱-质谱法测定土壤中18种有机氯农药

采用微波萃取-Florisil固相萃取柱净化分离、气相色谱和气相色谱-质谱相结合的方法测定土壤中的痕量半挥发性有机氯农药。优化了微波萃取和固相萃取柱净化条件,在最优条件下18种有机氯农药(α-HCH、β-HCH、γ-HCH、δ-HCH、七氯、艾氏剂、环氧七氯、硫丹Ⅰ、p,p′-DDE、狄氏剂、异狄氏剂、硫丹Ⅱ、p,p′-DDD、o,p′-DDT、异狄氏剂醛、硫丹硫酸酯、p,p′-DDT、甲氧滴滴涕)的回收率在89.56%~114.22%。对气相色谱和气相色谱-质谱法的仪器检出限、回收率、精密度和方法检出限进行对比,确定了采用气相色谱-质谱定性和气相色谱定量相结合的方法,测定实际土壤样品中的有机氯农药,使得定性和定量的准确度都得到提高。     

Spatial distribution, source analysis, and ecological risk assessment of DDTs in typical wetland surface soils of Poyang Lake

Dichlorodiphenyltrichloroethane (DDT) is a typical organic compound characterized by high bioaccumulability, toxicity, and persistence in the environment. To analyze the distribution and sources of DDTs in Poyang Lake, which is an important congregation site for migratory birds, the topsoils from five typical wetlands were sampled to evaluate the ecological threat posed by DDTs to organisms. The results show that as much as 56.1 % of the DDTs detected in this study comprises dichlorodiphenyldichloroethylene (DDE), the aerobic metabolism of DDT. The o,p′-DDT:p,p′-DDT ratio was higher than 0.2, which suggests that there was fresh influx of DDT from the pesticide. These results indicate that DDE was the main component among the metabolisms of DDTs and that the usage of dicofol might introduce DDT into the environment of Lake Poyang in a stealth form. However, an ecological risk assessment shows that the DDTs content in this region poses a low ecological risk.     

Adsorption efficiency,thermodynamics and kinetics of Schiff base-modified nanoparticles for removal of heavy metals

Nanosilica particles modified by Schiff base ligands 3-methoxy salicylaldimine propyl triethoxysilane (MNS₁), 5-bromo salicylaldimine propyl triethoxysilane (MNS₂) and 3-hydroxy salicylaldimine propyl triethoxysilane (MNS₃) were prepared, and their potential for separation of copper, lead, zinc, cadmium, cobalt and nickel ions from aqueous solutions was examined. The effect of parameters influencing adsorption efficiency including aqueous-phase pH, amount of adsorbent, stirring time and initial concentration of the metal ions was assessed and discussed. Although MNS₁ and MNS₃ removed lead ions efficiently, all adsorbents showed strong selectivity toward copper ions. It was shown that, under some circumstances, MNS₃ decreased the amount of other ions, particularly cobalt, in the aqueous phase. The adsorbents were also applied for removal of copper and lead ions from real samples. Possible quantitative desorption of the metal ions loaded onto the adsorbents suggests their multiple uses in adsorption–desorption process. Investigation of temperature dependency of the process led to determination of the ΔH°, ΔS° and ΔG° values. This investigation indicates that the adsorption of copper ions onto the all studied adsorbents and lead ions onto MNS₁ and MNS₃ is endothermic. The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms were tested to describe the equilibrium data. Pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion equations were applied to study the kinetics of copper and lead adsorption onto the modified nanoparticles. This investigation indicates that the process for all adsorbents follows pseudo-second-order kinetics and suggests a chemisorption mechanism for the adsorption processes by the studied adsorbents.     

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Study on the adsorption kinetics of orthophosphate anions on layer double hydroxide

A kinetic study was conducted on the adsorption of orthophosphate anions on layer double hydroxide (LDH). The adsorption has proved itself to be a spontaneous endothermic process and is large in capacity and rate. The adsorption isotherm correlates well with the Freundlich model, and a rise in temperature will lead to an increase in adsorption efficiency. Additionally, the results suggested that the adsorption is an entropy-increasing process and is in good agreement with the pseudo-second order kinetics. The free energy (ΔG) of adsorption of orthophosphate onto LDH varies within the range of −1.75–−3.34 kJ/mol, the enthalpy (ΔH) varies by 7.96 kJ/mol and the entropy (ΔS) by 33.59 kJ/mol. The adsorption activation energy is 8.3 kJ/mol, showing that the adsorption of orthophosphate onto LDH is determined to be a physical adsorption.     

Adsorptive removal of Cu(II) and Pb(II) onto mixed-waste activated carbon: kinetic,thermodynamic, and competitive studies and application to real wastewater samples

This work aimed to investigate the adsorption characteristics, both kinetically and thermodynamically, of Cu(II) and Pb(II) removal from aqueous solutions onto mixed-waste activated carbon, as well as to study the competitive behavior found in mixed heavy metal solution systems. This study shows that activated carbon prepared from mixed waste is an effective adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions, with the aim of detoxifying industrial effluents before their safe disposal onto water surfaces. The adsorption process was characterized in terms of kinetic and thermodynamic studies. In addition, the influence of presence of Cu(II) and Pb(II) in a competitive system was investigated. The results showed that the maximum adsorption capacities were gained at a pH of 6 with a contact time of 180 min, a metal solution concentration of 300 ppm, and an adsorbent dose of 0.3 g/L. The adsorption process was found to follow a pseudo-first-order kinetic model. Thermodynamic parameters such as ΔG ^o, ΔH ^o, and ΔS ^o showed that the sorption process was spontaneous and endothermic in nature. A competitive study demonstrated the applicability of mixed-waste activated carbon to adsorb Cu(II) and Pb(II) from a solution of mixed metals. In addition, the adsorption capacity was found to be as effective as other adsorbents reported in the literature. The developed adsorptive removal procedure was applied for treatment of real wastewater samples and showed high removal efficiency.