沿海滩涂垦殖对土壤氮总转化速率的影响分析

滩涂湿地在吸收、转化和滞留氮、磷等营养元素方面具有重要功能。选取江苏东部沿海典型滩涂区,分别对垦殖时间为0、3、6、17、30、60 a的沿海滩涂进行采样,对相应的土壤氮总转化速率指标进行实验测定。结果表明,滩涂垦殖后,表征氮素活化过程的指标,如总矿化率、总硝化率、净矿化率和净硝化率等有所增加,而有利于氮固持的铵态氮同化率指标无显著变化,硝态氮同化率指标变慢;围垦期限超过30 a后,各氮总转化速率指标渐趋稳定。相关性分析表明,净矿化率、总矿化率、铵态氮同化率、净硝化率、总硝化率与围垦年限呈显著正相关(p<0.01),相关性系数分别为0.966、0.929、0.819、0.800、0.798;硝态氮同化率与围垦年限呈显著负相关(p<0.01),相关性系数为-0.685;除铵态氮外,全氮、硝态氮、pH值、有机碳均与各氮总转化速率指标呈显著相关关系(p<0.01)。滩涂垦殖后土壤理化性质指标的改变带来土壤氮总转化速率的变化,一定程度上破坏了土壤氮生态系统平衡。     

密云水库入库河流微生物群落演替对氮素形态转化的影响

密云水库是北京市重要的地表饮用水源地,但近年来,密云水库库区及入库河流中的总氮（TN）浓度呈现连年上升的趋势.以密云水库上游典型入库河流牤牛河为例,考察各形态氮素变化的空间分布规律,并从微生物群落组成和功能预测的视角,解析氮素形态的转化,以期为密云水库的氮污染治理提供科学依据.结果表明,密云水库上游除TN外,其余水质理化指标均满足我国地表水环境质量标准（GB 3838-2002）的Ⅱ类标准.入库河流TN浓度显著高于库区（P<0.05）,且以NO₃^--N为主,占比为77.7%~92.9%.半城子水库库区的C/N较高,有助于反硝化脱氮的发生,表现出一定自净能力.牤牛河水体和底质中微生物群落结构具有显著差异,呈现一定的空间分布特征,高NO₃^--N浓度是影响微生物群落结构演替的主要环境因子.牤牛河中存在大量硝化和反硝化功能微生物,反硝化菌相对丰度高于硝化菌,且均呈现出底质略高于水体的特点.牤牛河优势硝化菌和反硝化菌分别为Nitrosopumilus和Pseudomonas.PICRUSt2功能预测结果表明,牤牛河微生物氮代谢以NO₃^--N还原模块为主,且主要发生于水体中;硝化过程的功能基因在水体中的丰度最高,主要为narGH;而参与NO₃^--N还原反应的主要功能基因为底质中的异养反硝化菌（DNRA）所携带的nirBD,而反硝化模块的功能基因主要为nirK.     

特种纸行业水污染防治对策——以浙江省为例

以浙江省为例,深入分析特种纸行业发展现状及特点、水污染物排放控制水平和企业在执行国家现有污染物排放标准过程中存在的问题与原因。针对特种纸的特殊性,从完善造纸行业标准体系的角度,提出制定特种纸行业污染物排放标准,确定一厂一策的标准执行体系的建议;从提升产业污染控制水平及产业转型升级角度,提出按规模、分区域、分纸品确定转型重点,研究制定最佳可行技术导则,加快污染治理设施的提升改造,加强企业技改力度及提高清洁生产水平等对策与建议,以促进特种纸行业的可持续发展。     

黄骅港三期筒仓防煤体高温对策研究

黄骅港三期是单个容量3万吨共24座筒仓的超大型群仓储煤系统,储煤主要来自神华集团所属煤矿,少部分为外购协作煤,多属易自燃煤种。为更有效控制火灾隐患,通过工艺流程分析及危险因素提取,试运营期间数据分析等,研究了致使煤体高温的危险因素和对策。发现运输过程中出现因雨淋而产生润湿热,因粉尘积聚发热的危险;筒仓储煤曾出现数天内温度从10℃升高到45℃,筒仓内有毒有害气体可能超限的危险;输煤皮带可能跑偏引起摩擦生热的危险等。试运营期间针对性采取了喷洒抑尘剂,设置警报系统及检测装置,加强皮带机监控和管理等安全措施。     

Chemically modified silica gel with 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone: Synthesis, characterization and application as an efficient and reusable solid phase extractant for selective removal of Zn(II) from mycorrhizal treated fly-ash samples

1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone functionalized silica gel was synthesized and used as a highly efficient, selective and reusable solid phase extractant for separation and preconcentration of trace amount of Zn(II) from environmental matrices. The adsorbent was characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis,¹³C CPMAS NMR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and BET surface area analysis. The dependence of zinc extraction on various analytical parameters such as pH, type and amount of eluent, sample flow rate and interfering ions were investigated in detail. The material exhibited superior adsorption efficiency for Zn(II) with high metal loading capacity of 1.0 mmol/g under optimum conditions. After adsorption, the recovery (> 98%) of metal ions was accomplished using 1.0 mol/L HNO₃ as an eluent. The sorbent was also regenerated by microwave treatment in milder acidic environment (0.1 mol/L HNO₃). The lower detection limit and preconcentration factor of the present method were found out to be 0.04 μg/L and 312.5 respectively. The modified silica surface possessed excellent selectivity for the target analytes and the adsorption/desorption process remained effective for at least ten consecutive cycles. The optimized procedure was successfully implemented for the extraction of Zn(II) from mycorrhizal treated fly ash and pharmaceutical samples with reproducible results.     

Speciation of organic phosphorus in a sediment profile of Lake Taihu I: Chemical forms and their transformation

Organic phosphorus(nonreactive P,NRP)is a major component of P in sediments,but information about its chemical forms and dynamic transformation is limited.The chemical forms and dynamic behaviors of NRP in a sediment profile from Lake Taihu,a freshwater and eutrophic lake in China,were investigated.Five forms of NRP in the sediments were extracted based on a chemical fractionation technique,including easily labile NRP(NaHCO3-NRP),reactive metal oxide-bound NRP(HCl-NRP),humic acid-associated NRP(NaOH-NRPHA),fulvic acid-associated NRP(NaOH-NRPFA)and residual NRP(Res-TP).There were notable transformations with increasing sediment depth from the labile NaHCO3-NRP and NaOH-NRP pools to the recalcitrant HCl-NRP and Res-TP pools,which caused the NRP to become increasingly recalcitrant as the early diagenetic processes proceeded.Further analyses showed that the relative changes in contents of organic matter and reactive Fe oxides in the sediment profile triggered a competition for binding NRP fractions and led to the transformation of NRP.The results highlighted the importance of abiotic processes in regulating the diagenesis of organic P and its stability in sediments.     

Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh₃)₄ and Pd₂(dba)₃. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.     

土壤重金属污染现状调查与评价

土壤重金属通过发生溶解、沉淀、吸附、氧化等物理、化学一系列反应后,最终以多种形态存在于土壤中,在生物体内富集,或转化为毒性更大的甲基化合物。本文调查了部分矿区污染的基本情况和修复效果,提出了矿区重金属复合性污染产生的原因和亟待解决的问题。     

模拟酸雨下铅锌冶炼废渣重金属的静态释放特征

以株洲某铅锌冶炼废水中和渣为研究对象,开展不同初始pH值（3.0,4.5,5.6和7.0）模拟酸雨静态浸出实验,研究22d浸泡过程中废渣Cd、Cu、Pb和Zn等重金属的动态释放规律及其化学形态变化和矿物相变特征.结果表明,废渣具有较强的酸缓冲潜力,浸出液pH值稳定在6.20~6.66.Cu和Pb在浸泡初期释放较快,Cd和Zn释放相对较慢.浸出液Cd浓度随浸出时间增加而上升,Zn浓度呈波动变化,Cu和Pb浓度变幅较小.提高雨水酸度促进废渣中重金属的释放,浸出液Cd、Cu、Pb和Zn浓度范围分别为1.38~8.70,0~0.02,1.21~2.26和27.2~135mg/L,其中Cd、Pb和Zn浓度分别超过我国《铅、锌工业污染物排放标准》（GB 25466-2010）限值的26.6~173倍、1.42~3.52倍和17.1~89.0倍..重金属BCR顺序提取表明,浸出液中较高Cd和Zn浓度与其赋存高活性态比例一致,且酸雨促使残渣态Cd和Pb向活性态转化.XRD分析显示,pH=3.0酸雨处理22d后原废渣中Cd和Zn的赋存矿物相消失,PbSO₄谱峰增强,表明废渣重金属的释放受其赋存矿物相及次生矿物形成的影响.重金属释放率呈现出Cd （2.50%~15.8%）> Zn （0.41%~2.13%）> Pb （0.06%~0.10%）> Cu （0.0003%~0.11%）的趋势.自然堆存酸雨作用下废渣中Cd、Pb和Zn具有较大环境风险,需加强降雨淋滤污染防治管控.     

中国资源型城市转型对劳动力需求的影响

资源部门的自强机制导致城市人力资本集中于资源型产业,进而造成资源型城市中低技能劳动者增多,使新兴产业对当地劳动力需求下降。因此,资源型城市转型可能会导致城市面临失业问题。使用倾向得分匹配与双重差分结合的方法,探讨了《全国资源型城市可持续发展规划（2013—2020年）》对资源型城市劳动力需求的影响。为验证该影响的内在机制,分别根据教育水平和制造业占比对城市进行三重差分回归。结果显示：城市转型导致资源型城市劳动力需求下降6.9%;成熟型和衰退型城市的转型是导致需求下降的主要原因;检验发现,教育水平更高或制造业占比更高的城市受转型政策的影响更小,从而可以从侧面证明资源部门的自强机制使新兴产业对当地劳动力需求下降。