Occurrence and distribution of heavy metals and tetracyclines in agricultural soils after typical land use change in east China

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at ?20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg?kg^?1 and 22.9 μg?kg^?1, respectively, on average. The total Cu sequence was field mustard?>?vineyards?>?asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20–40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.     

Bioaccessibility of polychlorinated biphenyls in workplace dust and its implication for risk assessment

Human exposure to bioaccessible PCBs via indoor dust is limited around the world. In the present study, the workplace dust sample from commercial office, hospital, secondary school, shopping mall, electronic factory and manufacturing plant were collected from Hong Kong for PCBs analyses. Total PCBs concentrations ranged from 46.8 to 249 ng g⁻¹, with a median of 107 ng g⁻¹. Manufacturing plant showed the highest concentration among all of sampling sites. PCB 77 was found as the dominant congeners. The bioaccessibility of PCBs in small intestinal juice ranging from 8.3% to 26.0% was significantly higher than that in gastric condition, ranging from 4.8% to 12.4%. In addition, significant negative correlations (p < 0.05) were observed between K_OW and bioaccessibility for all workplace dust samples. Risk assessment indicated that the averaged daily dose of dioxin-like PCBs via non-dietary intake of workplace dust, considering the bioaccessibility of PCBs, were much lower than the TDI of dioxins (2.3 pg WHO-TEQ kg bw⁻¹ d⁻¹) established by Joint FAO/WHO Expert Committee on Food Additives.     

响应面法和神经网络优化Acinetobactersp．DNS32发酵基质

为了提高阿特拉津降解菌Acinetobactersp．DNS32的产量,分别采用响应曲面法和基于人工神经网络的遗传算法对阿特拉津降解菌DNS32发酵培养基中3个重要基质成分（玉米粉、豆饼粉、K：HPO。）进行优化研究。响应曲面法确定3种成分的含量为玉米粉39．494g／L,豆饼粉25．638g／L和K。HPO。3．265g／L时,预测发酵活菌最大生物量为7．079×10^8CFU／mL,实测量为7．194×10^8CFU／mL;人工神经网络结合遗传算法优化确定3种主要成分含量为玉米粉为39．650g／L,豆饼粉为25．500g／L,K2HPO4为2．624g／L时,预测最大值为7．199×10^8CFU／mL,实测量为7．244×10。CFU／mL;最终确定培养基配方：玉米粉为39．650g／L,豆饼粉为25．500g／L,K2HPO4为2．624g／L,CaCO3为3．000g／L,MgSO4·7H2O和NaCl均为0．200g／L;优化后阿特拉津降解菌DNS32发酵生物量比优化前提高了36．6％。结果表明,在阿特拉津降解菌DNS32发酵培养基组分优化方面,响应面法和基于人工神经网络的遗传算法都是可行的,基于人工神经网络的遗传算法具有更好的拟合度和预测准确度。     

碘掺杂Ti02可见光光催化性能研究

在低于100℃温度条件下,采用溶胶一凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂（I-TiO2）,运用x-射线衍射（XRD）、透射电镜（TEM）及x-射线光电子能谱（XPS）等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下（A〉420nm）以罗丹明B（RhodamineB,RhB）的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为n1：n^ti=0．05：l,焙烧温度为400℃,降解介质条件pH=7时,l-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱（IR）,总有机碳（TOC）跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚（4-CP）的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生·OH高活性氧化物种从而氧化降解目标化合物。     

天然和CPB改性沸石对Hg^2＋的吸附特征

通过静态实验研究溴代十六烷基吡啶（CPB）改性沸石和天然沸石对废水中Hg^2＋的吸附特性,探讨了吸附动力学、吸附平衡和吸附热力学机制。研究表明：Langmuir方程能较好地描述2种沸石对Hg^2＋的吸附,CPB改性沸石对Hg^2＋的吸附率得到显著提高。实验条件下,改性沸石对Hg^2＋的吸附率从67．5％提高到98．9％,吸附容量从0．521mg／g提高到3．07mg／g。利用准一级动力学方程、假二级动力学方程、颗粒内扩散模型和Elovich方程分别对动力学过程进行拟合,发现2种沸石对Hg^2＋的吸附均满足假二级动力学方程,且离子的颗粒内扩散对整个吸附过程有影响。动力学拟合、D-R方程拟合和热力学研究综合表明：2种沸石对Hg^2＋的吸附既存在化学吸附又存在物理吸附,吸附吉布斯自由能变（△G^0）、焓变（△H^0）、熵变（△S^0）均小于0,反应为自发的放热反应,低温有利于吸附的进行。     

膜电解法在线再生酸性蚀刻液及回收铜新技术

采用极化曲线法研究了酸性蚀刻液阴、阳极电化学行为,并构建了离子膜电解反应体系,考察了在线再生酸性蚀刻液及回收铜的效果。结果表明,阳极氧化过程发生浓差极化,存在极限电流密度,Cu＋含量越高,极限电流密度越大;阴极还原分4步反应进行,存在极限电流密度;强化溶液传质可有效提高阴、阳极极限电流密度,有利于避免电解过程中析出氯气和氢气;在线实验表明,通过监控阳极液ORP,可避免析出氯气;分步降低电流电解有利于避免析出氢气,形成致密的金属铜块;在电流为9～24A范围内分4步电解23．5h可再生酸性蚀刻液23．5L,同时电沉积回收510g铜,纯度高达99．98％。阴极电流效率达到95．2％,吨铜电耗3251kWh。电解过程中无氯气和氢气析出,无废液排放,表明膜电解法在线再生酸性蚀刻液具有良好的应用前景。     

湿法净化黑烟中添加剂对炭黑沉降性能的影响

湿法净化黑烟中炭黑颗粒物的关键在于降低吸收液的表面张力并以高性能絮凝剂使其从溶液中絮凝、沉降以利于分离。选用十六烷基三甲基溴化胺(CTAB)为主要表面活性剂,使之与十二烷基苯磺酸钠(SDBS)和月桂醇聚氧乙烯(9)醚(AEO-9)进行复配实验,研究了复配液的表面张力,再向最低表面张力的复配表面活性剂溶液中投加絮凝剂聚合氯化铝(PAC)和聚丙烯酰胺(PAM),探讨絮凝剂的添加对黑烟颗粒沉降和絮凝的影响.实验结果表明:同时添加表面活性剂CTAB,SDBS和PAC,并使之浓度分别为0.5 mmol/L,0.4 mmol/L和200 mg/L时,炭黑颗粒的沉降效果最好,沉降率高达94%,且絮凝体较大,沉降时间仅为2 min。     

响应面法和神经网络优化Acinetobacter sp. DNS32发酵基质

为了提高阿特拉津降解菌Acinetobacter sp.DNS32的产量,分别采用响应曲面法和基于人工神经网络的遗传算法对阿特拉津降解菌DNS32发酵培养基中3个重要基质成分(玉米粉、豆饼粉、K2HPO4)进行优化研究。响应曲面法确定3种成分的含量为玉米粉39.494 g/L,豆饼粉25.638 g/L和K2HPO43.265 g/L时,预测发酵活菌最大生物量为7.079×108CFU/mL,实测量为7.194×108CFU/mL;人工神经网络结合遗传算法优化确定3种主要成分含量为玉米粉为39.650 g/L,豆饼粉为25.500 g/L,K2HPO4为2.624 g/L时,预测最大值为7.199×108CFU/mL,实测量为7.244×108CFU/mL;最终确定培养基配方:玉米粉为39.650 g/L,豆饼粉为25.500 g/L,K2HPO4为2.624 g/L,CaCO3为3.000 g/L,MgSO4.7H2O和NaCl均为0.200 g/L;优化后阿特拉津降解菌DNS32发酵生物量比优化前提高了36.6%。结果表明,在阿特拉津降解菌DNS32发酵培养基组分优化方面,响应面法和基于人工神经网络的遗传算法都是可行的,基于人工神经网络的遗传算法具有更好的拟合度和预测准确度。     

高效阿特拉津降解菌株DNS10降解条件优化

从长期施用阿特拉津的寒地黑土耕层(0～10 cm)土壤中筛选到一株能以除草剂阿特拉津为氮源生长的降解菌株,结合16S rRNA序列分析结果,将该菌株命名为Arthrobacter sp.DNS10。在接种量为108CFU/mL的条件下,菌株DNS10在24 h内对100 mg/L阿特拉津的降解率为99.41%。单因子实验结果表明,菌株DNS10适宜生长和降解的条件范围是:温度25～35℃,pH值5.0～8.0,培养液盐度0.1%～2%,对阿特拉津最大耐受浓度可达1 200 mg/L。正交实验法进一步表明,该菌株保持较好生长及降解能力的最优方案是温度30℃,pH值7.5,培养液盐度0.5%。影响其降解能力的环境因素的主次顺序依次是:温度>盐度>pH值。     

萃取净化电镀含镉废水

研究了二壬基萘磺酸(DNNSA)形成的微乳液从模拟含镉废水中萃取镉离子的工艺条件。分别考察了相体积比(O/A)、萃取时间、温度及萃取剂浓度对废水中镉离子萃取的影响。结果表明,萃取平衡时间为10 mim,降低温度及增加萃取剂浓度均有利于萃取。紫外光谱证实当DNNSA萃取镉时,所形成萃合物对萘环的结构无影响,且不会破坏微乳相的结构;分子荧光光谱表明镉离子对配体DNNSA有荧光猝灭作用。