Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

镉—5—Br—PADAP—溴化十六烷基三甲基铵—十八醇聚氧乙烯(20)醚显色体系的研究及应用

本文研究了镉-5-Br-PADAP-溴化十六烷基三甲基铵-peregalo显色体系的光谱特征,显色条件,络合物的组成、干扰及其消除。实验证明该法灵敏度高,ε=1.3×10~5l·mol~(-1)·cm~(-1)。选择性较好,显色酸度范围较宽pH=8.0-9.5,络合物最大吸收波长为560nm,镉在0-10μg/25ml的含量范围内服从比尔定律。经标准水样、工业废水及生活用水验证,不经分离可测定水中PPb级的微量镉。     

Influence of Temporal Variations in River Discharge, pH, Alkalinity and Ca on the Speciation and Concentration of Heavy Metals in Some Mining Polluted Rivers

Dissolved (dialysis in situ) and total concentrations ofCu, Zn, Cd and Al in eight mining polluted rivers in the Røros area, central Norway, were determinedby atomic absorption spectrometry (flame and graphite furnace) and compared to pH, Caconcentration and alkalinity through seasonal variations in river discharge. Totalconcentrations of the metals were highest during early spring flood and during summer andautumn rain episodes. Dissolved concentrations also increased as the spring floodproceeded, but small discharge peaks within this 2 month period as well as a considerableautumn flood episode appeared to lower rather than to raise the dissolved metal concentrations.Consequently the dissolved fractions of Zn, Cd and Al showed a significant negative correlationwith river discharge, and were low at the discharge peaks. Possibly high sediment concentrationsoccurring at high flood conditions more than counteracted desorption induced by pHdecrease, and led to decreased dissolved fractions through adsorption. Cu speciationon the other hand seemed to be more closely linked to pH. Alkalinity and Ca concentration,both assumed to protect aquatic life from metal pollution, were significantly lowerduring episodes with high Cu and Al total concentrations.     

土壤中铅铜锌镉的吸附特性

以徐州王庄矿（WZK）、奎河（KH）、背景-1（BG-1）和背景-2（BG-2）等4个土壤样品为供试对象，加入不同浓度梯度的铅、铜、锌、镉离子，通过静态实验研究了铅、铜、锌、镉的吸附特性。结果表明，土壤对4个重金属的吸附量与加入到土壤中的重金属离子浓度呈正相关性，它们之间大部分满足线性相关关系。在4个土壤样品中加入铅、铜、锌、镉离子的初始浓度比为10：10：10：1时，平衡浓度为Czn〉Ccu〉CPh〉Ccd，吸附量为Scd〉SPh〉Scu〉Szn，4个土壤样品对铅、铜、锌、镉离子的吸附能力依次为WZK〉KH〉BG-2〉BG-1。在所选实验条件下，土壤对铅、铜、锌、镉的吸附能力受土壤中铅、铜、锌、镉的含量、土壤有机质含量、阳离子交换量、土壤饱和含水量和土壤的pH值影响较大。     

滇池水中铝的形态分布初探

采用铬天青S光度法对滇池水中的总铝和各主要形态铝进行分析，并利用简单易行的紫外吸收表征水中有机物污染程度和颗粒物含量，初步探讨了各因素的变化对铝形态分布的影响。     

Quantitative biostratigraphy and species evolutionary sequence

Introduction of species evolutionary sequence into the quantitative biostratigraphy is a significant work, either for studying biologic evolution or for making stratigraphic correlation and reconstructing geologic history. The quantitative biostratigraphy is to determine biostratigraphic event sequences by using probabilistic analysis. The evolutionary sequence systematics can efficiently ascertain species evolutionary sequences. Two methods have been proposed to determine the sequence of species-disappearance events: (1) species extinction events can be closed by last occurrence events using quantitative biostratigraphic analysis; (2) the duration of a species may be approximately replaced by the duration of its parent species. To combine these two methods for determining the sequence of species disappearance is the best way up to now. A consulting standard sequence that consists of the speciation sequence of Permian waagenophylloid corals and the biostratigraphic event sequence of other important fossils in Permian is used as an example. The group spearman rank-correlation test is used to test the consulting standard sequence by comparing four types of calculations and two kinds of sequences and to find abnormal events. Based on the found abnormal events in the test, the consulting standard sequence is revised to deal with different conditions. Sequences of speciation and species-disappearance, and species duration are determined. Application of species evolutionary sequence to quantitative biostratigraphy can largely improve the quality of biostratigraphic event sequence. In stratigraphic correlation, furthermore, event sequences have higher precision than range biozones.     

Free cupric ion concentrations and Cu complexation in selected Swiss lakes and rivers

[Cu²⁺] and Cu complexation parameters in some selected freshwater systems in Switzerland were determined by the technique of ligand-exchange and DPCSV. Results from the water columns of some eutrophic and oligotrophic lakes are presented and compared to small acid lakes. Cu is strongly complexed by organic ligands which with very high stability constants at low concentrations are probably biologically produced, as indicated by the seasonal variations in the eutrophic lakes and by the relationship between Cu complexation and algal activity in the eutrophic (pCu=15–16), oligotrophic (pCu=13–14) and acidic (pCu=9–10) lakes. The extent of Cu complexation in river waters was generally lower than in the eutrophic lakes, at similar DOC levels. No obvious correlation between Cu complexation and DOC was observed, indicating that Cu complexing ligands are specific organic compounds.     

U.S. Mussel Watch: 1977–1978 results on trace metals and radionuclides

The results of the U.S. Mussel Watch Monitoring Program for the period 1976–1978 for trace metals and artificial radionuclides in bivalves are presented. The substances analysed included Ag, Cu, Zn, Cd, Ni, Pb, ²³⁸Pu, ^239+240Pu and ²⁴¹Am. The analyses of organic substances will be presented elsewhere. The concentrations of these substances in the bivalves may reflect upwelling processes, anthropogenic inputs or natural levels. Off the California coast, mussels show markedly elevated Pu and Cd concentrations in coastal areas adjacent to the most intensive upwelling zones. Elevated levels of Pb, for example, are found in organisms living adjacent to highly urbanized places. The general patterns of distribution repeat themselves year after year at a given site. Thus, it is concluded that annual monitoring activities may not be necessary and that a frequency of sampling of several or so years may be more appropriate to identify pollution problems. Finally, national or regional baselines for metal concentrations in bivalves from unpolluted waters are proposed. National baselines for Pb in the west coast mussels of 1·0 parts 10^?6 and for Ag in east coast mussels of 0·05 parts 10^?6 are suggested.     

The behaviour of dissolved arsenic in the estuary of the River Beaulieu

The chemical forms and distribution of dissolved arsenic species in the estuary of the River Beaulieu (Hampshire, U.K.) are reported. ‘Inorganic arsenic (V)’ in both the marine and riverine estuary inputs are in true solution, passing through ultrafiltration membranes having a nominal molecular weight cut-off of 500 daltons. Extensive removal of dissolved ‘inorganic arsenic (V)’ is apparent from the distribution of arsenic in the estuary, with laboratory mixing experiments indicating that removal is favoured in the low salinity region. ‘Inorganic arsenic (III)’ and methylated arsenic species account for up to 41% and 70% of the dissolved arsenic, respectively, but are only found during the warmer months when water temperatures exceed ca. 12°C.