湖南省四水流域水沙周期特征及其影响因素分析

采用复小波变换和M K非参数检验的方法分析了湖南省四水流域主要控制站1951~2011年径流量与输沙量周期规律和突变特征。结果表明：(1)湖南四水径流量存在多个波动增加和波动减少的波动变化现象,但无显著变化趋势;而输沙量虽然有一定的波动,但总体上呈波动减少变化态势,而且下降趋势较显著;(2)湘潭站、桃江站和桃源站径流量和输沙量存在20~25 a的第一主周期,而石门站径流量和输沙量的第一主周期不具有一致性,径流量主周期为2 a,输沙量主周期为13 a,但其径流量和输沙量第二、三主周期变化规律相吻合,均为3~5 a的周期;(3)大量的水利工程建设是导致输沙量减少的主要原因,径流量的变化与降水的变化规律较为一致     

春季香溪河库湾CODMn时空分布及其影响因子初探

于2012年春季在香溪河库湾合理布置断面观测,分析水体高锰酸盐指数(CODMn)的时空分布特征,并对CODMn与水体中叶绿素a、溶解氧(DO)、水体垂向稳定系数、总氮(TN)和溶解性硅酸盐(D Si)进行相关分析,以期为香溪河流域有机污染的治理提供支持和指导。结果表明：春季香溪河库湾CODMn浓度变化范围为1.40～5.36 mg/L,4月CODMn均值明显高于3月和5月,为366 mg/L,整个春季CODMn浓度从下游至上游呈现明显增大的趋势。相关分析发现,春季水华暴发期间,CODMn与叶绿素a显著正相关(分别为072和074),而在未暴发水华的3月二者的相关性不显著。浮游植物和水体稳定系数是影响CODMn变化的主要因素。倒灌异重流使得高含氮、低CODMn浓度的长江干流水体进入库湾下游并稀释CODMn浓度。CODMn与DO在3月和5月的弱相关关系为香溪河CODMn特殊的分布特征提供了其它合理的解释,其分布特征受多种因素的共同影响。春季库湾上游有机污染趋于恶化,限制支流特别是上游污染物的排放是改善有机污染现状的有效途径     

水温分层对香溪河库湾浮游植物功能群季节演替的影响

三峡水库水环境问题近年来引起社会广泛关注,以浮游植物功能群为基础,通过对2010年1~12月香溪河库湾水温、浮游植物等进行跟踪监测,探究支流库湾浮游植物群落结构演替趋势及其影响因子。结果表明：香溪河库湾2010年共出现18个浮游植物功能群,其中B、X1、P、Y、X2、D、LO、J、MP、G是代表性功能群;水温分层的季节性发育和消失是浮游植物群落结构演替的主要影响因素;冬季以耐受水温及光照限制的CS/S策略藻种为主;春季弱分层时,CR/R策略藻种适宜生长;夏季汛期时,呈现CR/R/C/CS多种策略藻种混生格局,强分层时,适宜稳定生境的S型策略藻种占据优势;秋季分层被打破,群落结构演替为耐受频繁波动环境的R型群落格局占优势     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Reproduction and biochemical responses in Enchytraeus albidus (Oligochaeta) to zinc or cadmium exposures

To better understand chemical modes of action, emphasis has been given to stress responses at lower levels of biological organization. Cholinesterases and antioxidant defenses are among the most used biomarkers due to their crucial role in the neurocholinergic transmission and in cell homeostasis preventing DNA damage, enzymatic inactivation and lipid peroxidation. The main goal of this study was to investigate the effects of zinc and cadmium on survival and reproduction of E. albidus and to assess metals oxidative stress potential and neurotoxic effects at concentrations that affected reproduction. Both metals affected the enchytraeids’ survival and reproduction and induced significant changes in the antioxidant defenses as well as increased lipid peroxidation, indicating oxidative damage. This study demonstrates that determining effects at different levels of biological organization can give better information on the physiological responses of enchytraeids in metal contamination events and further unravel the mechanistic processes dealing with metal stress.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

Interactions between accumulation of trace elements and macronutrients in Salix caprea after inoculation with rhizosphere microorganisms

Although the beneficial effects on growth and trace element accumulation in Salix spp. inoculated with microbes are well known, little information is available on the interactions among trace elements and macronutrients. The main purpose of this study was to assess the effect of phytoaugmentation with the rhizobacteria Agromyces sp., Streptomyces sp., and the combination of each of them with the fungus Cadophora finlandica on biomass production and the accumulation of selected trace elements (Zn, Cd, Fe) and macronutrients (Ca, K, P and Mg) in Salix caprea grown on a moderately polluted soil. Dry matter production was significantly enhanced only upon inoculation with Agromyces sp. Regarding the phytoextraction of Cd and Zn, shoot concentrations were mostly increased after inoculation with Streptomyces sp. and Agromyces sp. + C. finlandica. These two treatments also showed higher translocation factors from roots to the leaves for both Cd and Zn. The accumulation of Cd and Zn in shoots was related to increased concentrations of K. This suggests that microorganisms that contribute to enhanced phytoextraction of Cd and Zn affect also the solubility and thus phytoavailability of K. This study suggests that the phytoextraction of Zn and Cd can be improved by inoculation with selected microbial strains.