珠江口海区水产经济种类中重金属含量的初步分析

有关经济鱼类重金属含量的调查研究及海洋生物基线值(Baseline value)国外已有不少的报导。我所于1976—78年参加了珠江口近海区水产经济种类及底栖生物的污染调查,并对这一海域的环境质量作出了初步的评价。1978—79年又开展了珠江口外海     

珠江口及近海沉积有机质来源判断

用二元混合模型对有机地球化学指标之间的关系进行模拟,结果表明珠江口和近海沉积物样品OC/N与δ15N在早期成岩过程中均发生了较大改变,OC/N可用作判断有机质来源的辅助证据,而δ15N不宜用作沉积有机质来源的指示.δ15Corg 则可以较可靠地用来评价来源的贡献.稳定C同位素二元混合模拟结果表明从珠江河流出海口往近海方向,陆源有机质所占比例呈下降趋势,在珠江口内,陆源有机C的比例略大于水生有机C,而近海有机质以当地水生藻类为主要来源.     

2010年夏季珠江口海域溶解氧的分布特征和海气交换通量

根据2010年8月的调查资料,分析了珠江口海域溶解氧的分布特征,探讨了其与水体稳定性、营养盐、叶绿素a及CO2分压的关系。结果表明,溶解氧浓度由珠江口内向口外近海逐渐递增,在垂向上则随着水深由浅至深呈下降趋势。相关性分析显示,溶解氧在表底层的浓度差与温度差、盐度差和叶绿素a含量差都达到显著相关的水平,低氧区的形成与水体层化和有机质的降解耗氧密切相关,其中珠江冲淡水为浮游植物的生长和繁殖提供了丰富的N、P营养盐,而浮游生物的消亡和有机质的分解加剧了氧的亏损。溶解氧海气通量呈现明显的空间差异,其中河口上游表现为氧汇,而下游海域为氧源。     

珠江口及南海北部近海海域大气有机氯农药分布特征与来源

分冬、春航次采集了珠江口及南海北部近海海域大气样品,同时以广州和中山作为陆基对照点,对大气中的有机氯农药（OCPs）进行了系统分析.结果表明,大气中的有机氯农药主要为HCHs、DDTs和氯丹,其含量范围分别为 13～99、 73～390、 63～224 pg/m³（冬季航次）和10～106、 429～1 003、 1 724～9 638 pg/m³（春季航次）.总体而言,春季航次期间的大气OCPs含量普遍高于冬季航次.研究发现,珠江口及南海近海海域大气OCPs主要受控于陆源污染的影响,呈现近陆点高和远陆点低的特点.大气中 α-HCH的含量已显著降低,而高含量 γ-HCH的检出与林丹的继续使用有关,“新”DDT的污染主要来自三氯杀螨醇的生产和使用以及船舶防污油漆中使用的滴滴涕.春季航次期间大气氯丹含量的高值,源于白蚁高发期氯丹的大量使用以及来自西太平洋地区的大气长距离输送.     

珠江口水体表观光谱特性与类型分析

珠江口海域是典型的二类水体,光谱特性复杂,一直是国内学者研究的热点区域。本文基于2014年春（5月）、夏（8月）、秋（11月）、冬（2月）珠江口海域四个航次实测的表观光谱资料,探讨了珠江口海域遥感反射率的类型及时空分布特性。结果发现珠江口海域四季水体遥感反射率呈5大类型,每一类光谱都具有典型的区域性和季节变化特征,其谱峰在450~575 nm范围内随季节变化而移动,A类型常年分布在珠江口内,B类型冬春季节分布在珠江口外混合过渡类水体中,C类型主要分布在珠江口口门外水深较深的离岸海域,D类型春夏季在万山群岛附近海域出现,E类型与大洋水体的光谱特征类似。分析表明5种光谱类型的谱型变化趋势由不同的水质因子主导。该研究对深入探讨珠江口等我国近海二类复杂水体的光谱特性及其水色要素的遥感反演具有重要的参考价值。     

珠江口东海域营养盐比例及其对藻类的影响

根据珠江口东四口门(虎门、蕉门、洪奇门、横门)海域的调查资料,对营养盐含量和比值与浮游植物生长和种群结构的关系进行分析。结果表明:调查海域浮游植物的生长与海水中营养盐的浓度及营养盐之间的比例均有关,丰富的氮、磷、硅和较高的N:P、Si:P、Si:N比,可能是形成目前调查海域浮游植物群落以硅藻类占优势的种群结构的主要原因;但是在像深圳湾这样的半封闭海湾,营养盐含量及其之间的比例发生变化(尤其是N:P),将对浮游植物种群结构产生相应的影响。     

深圳湾及邻近沿岸沉积物中碳、氮和磷的分布

依据1998~2014年每年2个航次取得的资料,分析和研究了深圳湾和珠江口东南沿岸表层沉积物中生物地球化学要素[包括总碳(TC)、总有机碳(TOC)、总氮(TN)和总磷(TP)]的时空分布,并依据C:N原子比探讨沉积物中有机质的来源.结果表明,TC、TOC、TN和TP含量在深圳湾中分别为(13200±3600)、(12200±3200)、(910±352)和(594±288)mg/kg,而在珠江口东南沿岸中分别为(12000±3900)、(8700±2300)、(601±259)和(334±119)mg/kg.1998~2014年研究海区沉积物中TC和TN含量的年际变化均呈上升趋势,而TOC含量则呈下降趋势.研究期间TP含量在深圳湾中呈下降趋势,而在珠江口东南沿岸中呈上升趋势.深圳湾和珠江口东南沿岸中TOC:TN原子比分别约为17.7和19.5,研究期间均呈下降趋势.研究海区中表层沉积有机质(SOM)是陆生和水生2种来源的混合输入,在深圳湾中以水生源为主,而在珠江口东南沿岸中以陆生源为主.1998~2014年研究海区中表层SOM从以陆生源为主逐渐转变为以水生源为主.     

珠江口及南海近海海域大气多环芳烃分布特征

分冬、春两次航次分别采集了珠江口及南海近海海域大气气溶胶样品和气相样品,同时以广州和中山作为陆基对照点,对16种EPA优控多环芳烃进行了分析.结果表明,大气PAHs主要以气态化合物为主,总PAHs(气态+颗粒态)的含量范围为49.6～256.6 ng/m3,平均120.7 ng/m3.珠江口海域大气颗粒态多环芳烃季节变化显著,冬、春航次大气颗粒态多环芳烃的含量分别为6.7～18.0 ng/m3和0.4～5.1 ng/m3,冬季航次期间大气颗粒态PAHs含量的高值主要源于大陆气流对城市群大气PAHs污染的输送,另外干冷的季节亦有利于PAHs向颗粒态的富集.与此相反,气态多环芳烃含量的季节差异不明显.在冬季,随东北季风携带的城市粉尘可以将大气中的气态PAHs捕获,而春季航次的大气PAHs主要来源于西太平洋地区的远程输送和PAHs的海-气交换作用.认为受控于季风活动的水、热因子组合特征,是影响珠江口海域大气PAHs含量与分布的主导因素.     

珠江口三维水质与底泥耦合模型的验证及应用

基于一维河网与三维河口耦合水动力模型,建立了可描述珠江口水体-底泥中营养盐动态变化的三维水质-底泥模型,利用1999年和2006年夏季观测数据对模型进行了验证,在此基础上,模拟分析了珠江口主要水质因子和底泥营养盐通量的分布特征,以及底泥通量对珠江口营养盐输入的贡献.验证结果表明,模型能较好地反映出水体和底泥中的营养盐及溶解氧浓度的时空分布特征,各水质因子的模拟值与观测值的相对误差均小于38%;另外,底泥营养盐通量的模拟值与文献报道的实测结果较为接近,表明模型能合理地刻画出底泥主要生化过程及通量变化特征.模拟结果显示,夏季珠江口氨氮(NH_4~+-N)和活性磷酸盐(PO_4~(3-)-P)通量主要从底泥向水体输送,底泥是水体氮磷元素的源,而硝态氮和亚硝态氮(NO_3~-+NO_2~-,NO23)的通量输送方向则与之相反,底泥呈现“汇”的效应;底泥营养盐通量主要从河口向外海递减,伶仃洋NH_4~+-N、NO23、PO_4~(3-)-P的通量变化范围分别为0.24~8.88、-10.06~-0.14、-0.37~0.41 mmol·m~(-2)·d~(-1),珠江口近海的通量变化范围分别为-0.01~4.14、-1.45~0.68、-0.12~0.09 mmol·m~(-2)·d~(-1).整体而言,底泥营养盐通量对珠江口营养盐输入有明显贡献,夏季经底泥释放进入水体的NH_4~+-N和PO_4~(3-)-P最大相当于陆源总氮、总磷输入量的12%和22%.     

珠江口毛颚类的生态研究

根据2002～2003年珠江口12个航次的调查资料,分析探讨了不同调查时间和区域毛颚类的种类组成、丰度变化及其环境因子的影响.以表层盐度(S)变化将调查海域划分三个区域:Ⅰ区(S<25)、Ⅱ区(2530).12个航次的调查结果表明:调查海域共出现毛颚类13种,Ⅱ区和Ⅲ区的种数一般多于Ⅰ区,皆以暖水种居多.其中2002年7月(夏季)、2003年1月(冬季)和4月(春季)的3个航次结果表明珠江口毛颚类的平均丰度为23 ind/m3, 三个区域的平均丰度比较为Ⅰ区(43 ind/m3)> Ⅱ区(15 ind/m3)>Ⅲ区(11 ind/m3),春夏季的丰度高于冬季.另外在Ⅰ区进行了9个航次调查的研究表明:Ⅱ区的毛颚类平均丰度较高,月份之间的丰度差别明显,沿珠江口由内往外丰度增加.百陶箭虫(Sagitta bedoti)和肥胖箭虫(Sagitta enflata)是珠江口毛颚类的优势种.盐度、温度和饵料浓度是影响珠江口毛颚类丰度变化的重要因素.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.