海口湾海水重金属的行为特征

本文对海口湾溶解态铜、铅、锌、镉进行了测定.铜的变化范围为:0.47～1.16μg/dm3,平均值为0.78μg/dm3;铅的变化范围为:0.94～2.36μg/dm3,平均值为1.36μg/dm3;锌的变化范围为:1.28～4.83μg/dm3,平均值为3.14μg/dm3;镉的变化范围为:0.005～0.072μg/dm3,平均值为0.030μg/dm3,Cu、Zn的溶解态含量在龙昆路生活污水排污沟口、秀英工业排污沟口及海甸溪口的测站相对较高,Pb、Cd溶解态含量较低,湾内各站平面分布较为均匀.它们的溶解态含量垂直变化趋势为:Cu、Pb、Zn底层大于表层,而Cd表层大于底层.对Cu、Pb、Zn、Cd的颗粒态含量也进行了测定,指出海口湾海水中的颗粒物对重金属的净化起一定作用.对铜的溶解态中的强络合态和不稳态铜也进行了研究,强络合态占总溶解态的比例均在85%以上,对生物起毒性作用有关的不稳态铜含量很低,均小于5nmol/dm3,表明目前海口湾海水中的重金属铜不会对生物生长产生影响.     

近岸表层海水中溶解态铅的研究

采用阳极溶出伏安法(ASV)对1999年10月采自浙江省三门湾健跳港表层海水中溶解态铅的形态进行了分析,结果表明:海水中游离态铅的浓度为2.2 nmol/dm3,有机配位态则可分为两类,即PbL1和PbL2;两类有机配位体条件稳定常数的对数(logKpcobnLd1,pb2 和logKpcobnLd2,pb2 )分别为8.4和9.1;两类有机配位体浓度(L1和L2)分别为37.4 nmol/dm3和52.7 nmol/dm3,将上述结果与以往三门湾海区研究中海洋生物急性毒性试验结果和不同介质中铅含量进行对比可知,浙江三门湾健跳港海区表层海水中溶解态铅浓度对海洋生物是安全的,但个别底栖生物物种中较高的铅含量已影响到人类的食用安全。     

日本以南西北太平洋溶解态铜、镉和镍的垂直剖面的讨论

本文报道了1990年10月日本以南海水重金属垂直分布的一些结果,讨论了溶解态铜、镉和镍的浓度同生物地球化学环境的关系.表层水中溶解态铜的浓度比500m以浅层的浓度高;在4000m以深,溶解态铜达最大值8.2nmol/dm3.溶解态镍的浓度由表层的3.4nmol/dm3变化到深层的8.5nmol/dm3.最高值出现于较冷的水体中.溶解态镉的垂直剖面属良好的营养盐型分布,溶解态镉与磷酸盐呈线性相关,原子比是△Cd:△N:△P=3.5×10-4:14:1.     

海水中磷氮不同形态的同时测定

采用过硫酸钾-硼酸-氢氧化钠混合试剂作为氧化剂,同时测定海水中总磷、氮和总溶解态磷、氮,从而建立了海水中磷、氮不同形态的分析流程及步骤。总磷、总溶解态磷浓度为0.35～1.09μmol/dm3时,相对标准偏差小于6.6%;总氮、总溶解态氮浓度为11.8～54.8μmol/dm3时,相对标准偏差小于5.6%。总磷、总溶解态磷和总氮、总溶解态氮的回收率分别为95.0%～106.0%和94.0%～106.0%。本文的分析方法可用于对近岸海水及河口水中磷、氮不同形态的同时测定。     

南极普里兹湾及其邻近海域溶解有机碳的分布

中国南极科学考察第16航次期间(1999年11月～2000年4月),在南极普里兹湾及邻近海域的不同站位与水深采集海水样品用于溶解有机碳测定,通过高温催化氧化法完成样品的分析.结果表明,在调查期间,南极普里兹湾及其邻近海域各测站上层水体(0～100m)溶解有机碳浓度的变化范围为14.3～181.1μmol/dm3,平均为52.5μmol/dm3,该变化幅度比Ross海、太平洋等海域的相应值略大.溶解有机碳垂直分布的特征是0大于25大于50大于100m,即随深度的增加溶解有机碳浓度逐渐减小,与生物活动在垂直方向上的强弱变化相关.根据200m以深水柱溶解有机碳的垂直分布,可确定研究海域难降解溶解有机碳的浓度为40.4μmol/dm3,与其他研究所报道的数值(～42μmol/dm3)相近.上层水体(0～100m)过剩溶解有机碳的空间分布显示,64°S以北海域溶解有机碳过剩较多,而64°S以南海域则过剩溶解有机碳较少.溶解有机碳浓度与分布特征显示,普里兹湾及其邻近海域溶解有机碳浓度与南大洋其他海域相当,具有低溶解有机碳的一般特征.溶解有机碳浓度的空间分布呈现由西南向东北方向逐渐增加的趋势,这可能与南极陆架夏季上层水的北向扩展有关.生物活动及水体运动是研究海域溶解有机碳分布的主要影响因素.     

胶州湾东部海水中氮的含量和分布

根据 1990年 11月到 1991年 8月胶州湾东部 4个航次的调查资料 ,讨论了各种氮的含量变化及分布情况 :溶解无机氮含量范围为 1.12～ 34 .8μmol/ dm3,年平均为 11.1μmol/ dm3。秋季硝酸氮为溶解无机氮的主要形式 ,占 68% ,平均为 11.2 μmol/ dm3。其他 3个季节氨氮含量最高。冬、夏两季溶解态有机氮含量分别占总氮的 69%和 66% ,是主要形态。其分布大致呈自东北向西南递减变化。     

基于切向超滤技术的胶体有机碳和无机氮分离及物源初探

利用切向超滤技术对九龙江口天然水体中胶体相(1 kDa～0. 45μm)、真溶解相(1 kDa)和"溶解相"(0. 45μm)的溶解有机碳和无机氮进行了分离与提取,初步探讨了水环境因子对其理化特性的影响机制,进而探讨了它们的来源和转化.结果表明,切向超滤过程的膜空白和质量平衡符合技术要求;溶解有机碳、亚硝酸盐氮、氨氮、硝酸盐氮和无机氮存在形式以真溶液相(1 kDa)为主,其在胶体相中的质量浓度分别为0. 207～0. 810 mg/dm3、0. 001～1. 870μg/dm3、ND～2. 08μg/dm3、0. 62～79. 30μg/dm3和1. 07～81. 10μg/dm3;胶体态溶解有机碳(COC)含量主要受陆源输入控制.     

离子色谱-电感耦合等离子体质谱联用测定海水中的IO_3~-和I~-

研究了离子色谱-电感耦合等离子体质谱(IC-ICPMS)联用技术直接进样测定海水中IO3-和I-的方法.采用IonPacAG23离子色谱保护柱分离IO3-和I-,以浓度4.0mmol/dm3的KOH为流动相,流量为1.0cm3/min,每个样品的分析时间为2.5min.采用2.5×10-3cm3的进样量,IO3-和I-的检出限分别达到0.6和0.4nmol/dm3,可满足海水中碘形态的定量分析.该方法的IO3-和I-浓度范围在2.0nmol/dm3～2.0μmol/dm3.     

渤海湾北部海域表层海水的表观铜络合容量

为给渤海湾北部海域重金属铜环境容量研究提供科学依据，采用阳极溶出伏安法对该海域12个站位表层海水样品的表观铜络合容量(ACuCC)和条件稳定常数(K)以及络合容量指数(CCI)进行了测定和计钟：。得到该海区表层海水的表观铜络合容量在228．0～673．4nmol／L之间，平均值为437．5nmol／L，条件稳定常数对数值(IgK)变化范围在7．41～8．84之间，平均值为7．89，络合容量指数在72．69％～92、92％之间，平均值为82．93％。表明该海域表层海水对重金属铜具有较强的络合能力。     

九龙江口水体中不同相态磷的环境化学行为研究

利用切向超滤技术分离和提取九龙江口水体中溶解相(粒径0.45μm)、胶体相(分子量 1 k Da,粒径0.45μm)和真溶解相(分子量1 k Da)的活性磷酸盐(SRP)和溶解态总磷(DTP),初步探讨了不同相中各形态磷的环境化学行为。研究表明,切向超滤过程的SRP和DTP系统空白分别为ND～0.001 mg/dm~3和ND～0.005 mg/dm~3,均未高于方法检出限;样品质量回收率为92.3%～100.0%,满足80.0%～120.0%质量技术要求。真溶解相中SRP、溶解态有机磷(DOP)和DTP占溶解相比例为65.3%～92.3%,存在形式以真溶解相为主;胶体相中SRP、DOP和DTP的含量分别为0.13～4.19、3.25～19.20μg/dm~3和3.39～23.40μg/dm~3,占溶解相比例为1.2%～17.0%;真溶解相和溶解相中的各形态磷含量主要受陆源输入控制。     

Behavior features of heavy metals in the Haikou Bay waters

INThonUCrIONBecause of the discharge of industrial waste water, waste residue, waste gas and acid rain theheavy metals concentration in river and lake and eventually in seawater have been increasing.Therefore many studies on heavy metals innuencing marine ecological environment have beencarried out (Sun et al., 1990; Sunda and Guillard, 1976; Zhu et al., 1992). After entering intothe sea, heavy metals change, transfer and transform, and these processes have gained attentionfrom marine envi…     

C18 Sep-Pak Extractable Dissolved Organic Copper Related to Hydrochemistry in the North-west Mediterranean

Extractable organic copper using C18 Sep-Pak cartridges was investigated in seawater after laboratory experiment showed that the (C18 Sep-Pak) cartridges were reliable, in open and coastal waters with normal levels of dissolved organic carbon, for the separation of a specific fraction of organo-copper complexes.Given that the Sep-Pak cartridges retain the hydrophobic fraction of the dissolved organic matter, this extraction technique was applied for studying the characteristics of this particular hydrophobic dissolved organic copper fraction (hDOCu) in the north-western Mediterranean waters. Surface distribution of hDOC is influenced by organic matter input from the river Rhone and its estuary as well as the physical processes affecting the primary productivity such as coastal upwelling. By correlating hDOCu concentrations with total dissolved copper and other hydrochemical data such as salinity and dissolved organic carbon, it was possible to examine the behaviour of hDOCu in the water masses of different sources and ages.Marine organic matter has been shown to have high complexing capacity. Productive superficial and intermediate waters as well as deep waters showed relatively high and comparable complexing capacity indicating that old organic matter may have strong complexing sites.     

海湾区海水中的溶存甲烷 Ⅱ.浓度、海气交换通量

本文基于日本东京湾、伊势湾和浜名湖的调查资料，详细地比较了这3个海湾海水中的溶存甲烷浓度、饱和度。表层海水中，溶存甲烷浓度以供名湖最高，达95nmol／dm3，伊势湾和东京湾相近，分别为41nmol／dm3和37nmol／dm3；其表层测定浓度是其平衡浓度的13～78倍，并分别计算了这3个海湾中甲烷的海气交换通量；用平均值外推法得出全球海洋环境中总的甲烷海气交换通量为6．3Tg／a。     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

A study on seawater apparent heavy metalcomplexation capacity in the Haikou Bay

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Organic and inorganic speciation of copper in the Irish Sea

The metal complexing ability of surface water of the Irish Sea has been measured by the MnO₂ adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO₃⁰ (60%), followed by CuOH⁺ (16%) and Cu(OH)₂⁰ (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%.     

Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions

A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10^?8 and 3.3 × 10^?8 M, and conditional stability constants (log K′_CuL) of 12.2 and 10.2, respectively.     

An experimental study on the speciation of dissolved zinc,cadmium, lead and copper in river rhine and north sea water,by differential pulsed anodic stripping voltammetry

Dissolved electroactive concentrations of zinc, cadmium, lead and copper in river Rhine and North Sea samples have been measured at natural and lower pH values by differential pulsed anodic stripping voltammetry using a Kemula-type hanging mercury drop electrode. Average concentrations detected in North Sea samples at salinities $\text{? 32‰ S}$ and their range are (in μgl^?1): 3.9 (2.0–7.5) for zinc, 0.23 (0.13–0.31) for cadmium, 0.3 (0.1–0.6) for lead and 0.3 (0.25–0.60) for copper (pH 8.1). The APDC-MIBK extracting/concentrating method, followed by AAS measurement applied to the same samples, resulted in 3.9 (2.0–7.5) for zinc, 0.11 (0.01–0.27) for cadmium, 0.5 (0.2–0.9) for lead and 1.6 (0.7–3.2) for copper. A fraction of the electroactive concentrations at pH 2.7 (6.1 for Zn) is electroactive at pH 8.1. The fractions are 100% for Cd, 20% for Cu, 13% for Pb and 40% for Zn. The remaining fractions are partly composed of organically bound species in solution. The low value for lead may be caused by the presence of particulate lead that is dissolved at low pH.Ionic copper and lead species, added separately to seawater at pH 8.1 are removed from the electroactive form, and taken up in (organic) complexes in the same ratio (at least for copper) as the species already present. Added ionic zinc is not removed within the time scale of the measurements (30 min). North Sea water at the natural pH has a complexing capacity, probably due to the presence of dissolved organic compounds, in a concentration equivalent to 3.10^?7M copper. The complexing capacity is zero at pH 2.7. The usual method of standard addition for the determination of electroactive copper and lead concentrations may lead to erroneous results in samples where complexation of this type occurs.     

海水中丙烯酸的高效液相色谱法建立及应用

建立了一种测定海水介质中丙烯酸的高效液相色谱法。采用耐纯水相和较低pH的Agilent SB-Aq-C18柱(100 mm×4.6 mm i.d.,5 μm), 0.35%磷酸溶液(pH=2)为流动相,使用紫外检测器,检测波长为210 nm,外标法定量测定。丙烯酸的保留时间在14.2~ 14.9 min,方法的检出限为4 nmol/dm3(S/N=3),在0.01~10 μmol/dm3的范围内均有良好的线性关系,相关系数可达0.999 6,加标回收率为95.4%~98.1%,相对标准偏差为1.3%~1.6%(1.04~2.32 μmol/dm3)。采用0.2 μm滤膜重力过滤冷藏的办法来保存海水丙烯酸样品。检测出2011年5月份青岛近海海水中丙烯酸的平均浓度为(0.101±0.069) μmol/dm3;海洋微藻球形棕囊藻在整个生长周期内培养体系中丙烯酸的浓度为0.339~2.219 μmol/dm3。