Sediment–water interactions of natural oestrogens under estuarine conditions

The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol⁻¹ was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (K_p^true) and colloidal particles (K_c^true) have been calculated, and a K_p^true value of 141 and 102 ml g⁻¹ was obtained for oestrone and 17β-oestradiol, respectively. In addition, K_c^true values for oestrone (222×10² ml g⁻¹) and 17β-oestradiol (135×10² ml g⁻¹) were two orders of magnitude higher than their respective K_p^true values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

安徽铜陵凤凰山夕卡岩型铜矿床中辉钼矿Re-Os同位素年龄及其地质意义

铜陵矿集区是我国长江中下游Cu-Au-Fe-Mo成矿带中最重要的有色金属基地之一,凤凰山矿床是铜陵矿集区的重要组成部分,为一个典型的夕卡岩型铜矿床。本文利用Re-Os同位素定年方法对凤凰山铜矿床进行了成矿时代测定,获得了辉钼矿的Re-Os同位素模式年龄范围为139.1±2.4～142.0±2.2Ma,等时线年龄为141.1±1.4Ma,与矿区内石英二长闪长岩和花岗闪长岩SHRIMP锆石U-Pb年龄(144.2±2.3Ma)相吻合,也与铜陵地区其他矿田的成矿时代基本一致,可能为岩石圈减薄事件的成矿响应。     

赣南营前岩体的年代学、地球化学、Sr-Nd-Hf同位素组成及其地质意义

赣南营前岩体由早期似斑状花岗闪长岩和晚期细粒黑云母花岗岩组成,在前者中普遍发育暗色基性包体。SHRIMP锆石U-Pb测年显示似斑状花岗闪长岩为172.2±3.1Ma,细粒黑云母花岗岩为168±3Ma,包体为167.6±3.3Ma。所有的岩石均为钙碱性系列,稀土元素显示LREE富集,HREE亏损,Eu负异常并不明显的特征,Nb-Ta负异常显示壳源物质的特征。晚期细粒黑云母花岗岩、早期似斑状花岗闪长岩、暗色包体的(87Sr/86Sr)i和εNd(t)值分别为0.70885～0.70965、0.71058～1.46393、0.70788～0.70923和-6.38～-5.31、-6.51～-5.17、-5.47～-4.31;锆石εHf(t)值分别为-12.4～-5.7、-9.2～-4.2、-9.4～+0.1。结合岩相学、地球化学研究,初步认为营前岩体的两期花岗质岩石源于地壳重熔,地幔底侵导致地壳熔融形成营前岩体,基性岩浆加入到未冷却的酸性岩浆中形成了目前所见到的暗色包体。结合区域上的研究资料,认为中侏罗世期间,沿"十杭"断裂带及与其相平行的一些深断裂发生了板块的撕裂,这些缝合带是岩石圈相对薄弱的地带,有利于幔源物质底侵上升以及壳幔相互作用。     

新疆阿尔泰克因布拉克铜锌矿床地质特征及成矿作用

克因布拉克中型铜锌矿床赋存于早二叠世花岗岩外接触带的上志留统-下泥盆统康布铁堡组黑云石英片岩、变质石英砂岩中。矿床的形成经历了夕卡岩期、热液期和表生期,铜锌矿主要形成于热液期。矿石中石英和方解石流体包裹体划分为H_2O-NaCl型和H_2O-CO_2(±CH_4/N_2)-NaCl型。成矿温度变化于146～448℃,在170℃、270℃和350℃出现峰值;流体盐度变化于0.2%～46.9%NaCl_(eq),峰值为1.5%NaCl_(eq)和5.5%NaCl_(eq);流体的密度0.55～1.19g/cm~3。硫化物的δ~(34)S集中变化于-8.4‰～1.9‰,峰值为0‰,表明硫来自岩浆。石英和方解石δD_(SMOW)介于-130‰～-79‰,δ~(18)O_(SMOW)值介于8.0‰～11.6‰,δ~(18)O_(H2O)值为-1.7‰～4.43‰,表明成矿流体主要是岩浆水,混合大气降水。方解石中δ~(13)C_(PDB)变化于-5.3‰～-1.1‰,暗示碳来自花岗质岩浆。成矿时代为早中二叠世,成矿作用与花岗质岩浆期后的热液活动有关。     

Palaeomagnetism of Holocene lake sediments from north Poland

Summary. Detailed palaeomagnetic investigations of 17 cores of Holocene lake sediments from four lakes in Poland show a pattern of declination variations similar to those found in Lake Windermere, England and in addition a well defined pattern of inclination variations. A total of nine inclination swings are observed compared to five declination swings and their phase relationships are such that both sets of swings cannot be periodic. Exact dating of the palaeomagnetic record is not possible as radiocarbon ages are over 1000 yr older than those deduced from palynological studies. Thermomagnetic and X-ray studies on magnetic concentrates confirm the results of studies of remanence cooling, IRM acquisition and coercivity experiments which are consistent with fine grained magnetite as the main magnetic mineral in the sediments.     

Concentration and subcellular distribution of trace elements in liver of small cetaceans incidentally caught along the Brazilian coast

Concentrations of trace elements (V, Cr, Mn, Fe, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, T-Hg, Org-Hg, Tl and Pb) were determined in liver samples of estuarine dolphin (Sotalia guianensis; n = 20), Franciscana dolphin (Pontoporia blainvillei; n = 23), Atlantic spotted dolphin (Stenella frontalis; n = 2), common dolphin (Delphinus capensis; n = 1) and striped dolphin (Stenella coeruleoalba; n = 1) incidentally caught along the coast of Sao Paulo State and Parana State, Brazil, from 1997 to 1999. The hepatic concentrations of trace elements in the Brazilian cetaceans were comparable to the data available in literature on marine mammals from Northern Hemisphere. Concentrations of V, Se, Mo, Cd, T-Hg and Org-Hg increased with increasing age in liver of both estuarine and Franciscana dolphins. Very high concentrations of Cu (range, 262-1970 microg/g dry wt.) and Zn (range, 242-369 microg/g dry wt.) were observed in liver of sucklings of estuarine dolphin. Hepatic concentrations of V, Se, T-Hg, Org-Hg and Pb were significantly higher in estuarine dolphin, whereas Franciscana dolphin showed higher concentrations of Mn, Co, As and Rb. Ratio of Org-Hg to T-Hg in liver was significantly higher in Franciscana dolphin than estuarine dolphin, suggesting that demethylation ability of methyl Hg might be lower in liver of Franciscana than estuarine dolphins. High hepatic concentrations of Ag were found in some specimens of Franciscana dolphin (maximum, 20 microg/g dry wt.), and 17% of Franciscana showed higher concentrations of Ag than Hg. These samples with high Ag concentration also exhibited elevated hepatic Se concentration, implying that Ag might be detoxified by Se in the liver. Higher correlation coefficient between (Hg+0.5 Ag) and Se than between Hg and Se and the large distribution of Ag in non-soluble fraction in nuclear and mitochondrial fraction of the liver also suggests that Ag might be detoxified by Se via formation of Ag2Se in the liver of Franciscana dolphin.     

Antifouling biocides in discarded marine paint particles

Antifouling paint fragments collected from marinas and leisure boat maintenance facilities and in the vicinity of abandoned boats have been chemically characterised. High concentrations of Cu (23-380 mg g⁻¹) and Zn (14-160 mg g⁻¹) in the samples (n = 14) are consistent with the use of these metals in the principal biocidal and non-biocidal pigments in contemporary antifouling formulations. Up to about 2% and 7% of the respective metals were solvent-extractable, suggesting that organo-forms of Cu and Zn (e.g. pyrithiones) were also present. Of the organic biocides, dichlofluanid was present in most samples and at concentrations up to about 20 mg g⁻¹. Chlorothalonil and Irgarol 1051® were only detected in one and four cases, respectively, and Sea Nine 211® was not detected in any sample. Results are discussed in terms of UK legislation regarding biocide usage and the likely effects and fate of discarded paint particles in coastal environments where boats are repaired or moored.