Effective AC and DC responses of nonlinear composites at higher concentration

For higher concentration of inclusions, an effective medium approximation (EMA) method is used to investigate the bulk effective response of weakly nonlinear composites, which are subject to the constitutive relation of electric displacement and electric field, D-alpha = epsilon E-alpha + chi(alpha)|E|(2) E. As an example of three dimensions, under the external AC and DC electric fields E-app = E-a (1 + sin omega t), we have derived the general effective nonlinear response of composites by the EMA method for higher concentration of spherical inclusions. Furthermore, the effective nonlinear responses at harmonics are predicted.

长江口上升流区营养盐动力学

近年来，东中国海赤潮灾情严重，且74.7%的赤潮集中在 30°30′～32°00′N、122°15′～123°10′E的“赤潮高发区”。在研究该区赤潮成因时，长江口沿岸上升流的影响越来越受到人们的关注，并被一些专家观测和研究。但目前为止，针对该区营养盐动力学特征及其对叶绿素a影响的研究较少，且不系统。 本文根据2004年四个季度月的调查资料，系统地探讨了长江口上升流区营养盐动力学特征；估算了上升流的营养盐通量，并和陆源输入通量进行了比较。初步探讨了上升流对该区营养盐结构和浮游植物生长的影响。为深入研究长江口富营养化和赤潮形成机制提供了参考。 结果表明春季在122°20′～123°00′E，31°00′～32°00′N以北海域存在低温、高盐、低溶解氧的沿岸上升流。它不但可把底层高含量磷酸盐输送到10m层以上海区，而且还为上层海区输入了相对低含量硝酸盐和硅酸盐，从而改善了上层营养盐结构，使得营养盐比值接近Redfield Ratios，同时还改善了上层的透明度；从而有利于浮游植物的繁殖。夏季上升流受到强大的长江冲淡水压制，表现不如春季明显，主体水团出现在122°20′～123°00′E，31°15′～31°50′N海区10m层以下。 在秋、冬季，上升流现象被更强的对流现象所掩盖，表现为台湾暖流表层水的入侵。表、底层水域不仅温、盐度分布十分接近，而且营养盐结构差异也较小。冬季台湾暖流水中的磷酸盐含量远比秋季高，与春、夏季上升流水团中磷酸盐含量接近。硝酸盐和硅酸盐含量比秋季稍高，比春、夏季上升流水团中的含量稍低。 叶绿素a季节性分布表明，在春、夏季的10m层以下水域，叶绿素a受到透明度限制，含量相差不大；而在表层和10m层之间，春季叶绿素a的含量远高于夏季，说明春季的营养盐结构和自然条件更有利于浮游植物的繁荣生长。在秋季台湾暖流水影响的区域，表层叶绿素a含量较夏季稍低。而冬季该区叶绿素a含量则是最低的。 对长江口上升流水团春季营养盐通量的计算结果表明，上升流水团中磷酸盐输送通量远远高于长江径流输入，是其径流通量的两倍以上，可能会成为影响该海区磷酸盐分布以及浮游植物生长的一个值得关注的因素。 关键词：上升流，营养盐动力学，营养盐结构，叶绿素a，长江冲淡水

Nutrient characteristics in the Yangtze River Estuary and the adjacent East China Sea before and after impoundment of the Three Gorges Dam

From November 2002 to 2006, five cruises were undertaken in the Yangtze River Estuary and the adjacent East China Sea to compare the nutrient concentrations, ratios and potential nutrient limitation of phytoplankton growth before and after impoundment (June 2003) of the Three Gorges Dam (TGD). Concentrations of dissolved inorganic nitrogen (DIN), soluble reactive phosphorus (SRP) and total nitrogen (TN) exhibited an increasing trend from 2002 to 2006. In contrast, total phosphorus (TP) concentration exhibited a decreasing trend. The mean concentrations of DIN, SRP, and TN in the total study area increased from 21.4 mu M, 0.9 mu M, and 41.8 mu M in 2002 to 37.5 mu M, 1.3 mu M. and 82.2 mu M in 2006, respectively. while TP decreased from 2.1 mu M to 1.7 mu M. The concentration of dissolved reactive silica (DRSi) had no major fluctuations and the differences were not significant. The mean concentration of DRSi in the total study area ranged from 52.5 to 92.3 mu M. The Si:N ratio decreased significantly from 2.7 in 2002 to 1.3 in 2006, while TN: TP ratio increased from 22.1 to 80.3. The area of potential P limitation of phytoplankton growth expanded after 2003 and potential Si limitation appeared in 2005 and 2006. Potential P limitation mainly occurred in an area of salinity less than 30 after 2003, while potential Si limitation occurred where the salinity was greater than 30. By comparison with historical data, the concentrations of nitrate and SRP in this upper estuary during November 1980-2006 increased obviously after impoundment of TGD but DRSi decreased. Meanwhile, the ratios of N:P, Si:N and Si:P decreased obviously. (c) 2009 Elsevier B.V. All rights reserved.

Pretreatment Method for Nitrogen Isotopic Analysis of Nitrate in Seawater

A suitable method for the pretreutment of dissolved nitrate samples in seawaters for nitrogen isotopic analysis was established. First, the seawater samples were processed by removing nitrite and amonium. Then Devard's alloy was added in sample for conversion of dissolved nitrate to ammonium. The sample was distilled, and then the ammonium condensate was collected with zeolite. after distillation, the collected condensate was filtered and prepared for determining nitropic values. Some tests of the method were conducted. The distillation condition, the influence of salinity on nitrogen isotopic analysis, absorption of ammonium onto zeolite and an improved method on a large volume of seawater were discussed in this study. The results showed that the distillation step had an average recovery of (104.9 +/- 4.2) % (n = 6) when distillating every 300 mL aliquot of the sample under a strong alkaline condition with 0.5 g devard's alloy and a distillation time of 30 min. The nitrogen isotopic fractionation decreased markedly when salinity was increased from 0% to 0.5%; further increase(1% - 3.5%) showed little effect. The adsorption rate of ammonium onto zeolite had a high yield of (95.96 +/- 1.08) % (n = 6) in average. An improved collection method was used to process a large volume of seawater with several distillations, and had good effect on analysis. The method had been applied to analyze water samples collected from Changjiang estuary. The analytical results indicate that the method is suitable for delta N-15 analysis of dissolved nitrate in seawaters. The present method could provide valuable information about the source and cycle mechanism of dissolved nitrogen in estuary waters.

The nitrogen isotopic composition of dissolved nitrate in the Yangtze River (Changjiang) estuary, China

The nitrogen isotopic composition of dissolved nitrate (delta N-15-NO3-) in surface water of the Yangtze River estuary was determined in four seasons of 2006. delta N-15-NO3- ranged from 0.4 parts per thousand to 6.5 parts per thousand and varied with seasons and geographic regions, reflecting the dynamics of nitrogen cycling in the estuarine ecosystem. delta N-15-NO3- was markedly lower in February than in other seasons and exhibited conservative mixing, which was probably attributed to the NO3- being sourced from the atmospheric deposition and agricultural fertilizer. In the upper estuary, the influence of riverine inputs was important during all surveys. in the turbidity maximum zone, nitrification was found with nitrate depleted in N-15 in May, whereas denitrification resulting in heavy delta N-15-NO3- played an important role in August. More enriched delta N-15-NO3- values coinciding with losses of nitrate concentrations based on the conservative mixing model were found in the adjacent marine area in May, and may reflect obvious phytoplankton assimilation of dissolved nitrate. In this manner, delta N-15-NO3- may be a sensitive indicator of nitrogen sources and biogeochemical processing existing in this estuary in conjunction with the variations of dissolved nitrate and other environmental factors. (C) 2009 Elsevier Ltd. All rights reserved.

Nutrient Dynamics in the Upwelling Area of Changjiang (Yangtze River) Estuary

Nutrient dynamics and its influence on the distribution of chlorophyll-a in the upwelling area of the Changjiang (Yangtze) River estuary were investigated in the spring (May) and summer (August) of 2004. In the spring, upwelling was apparent in the region of 122 degrees 20'-123 degrees 00' E, 31 degrees 00'-32 degrees 00' N and was associated with low temperature (16-21 degrees C), high salinity (24-33 practical salinity units [psu]), and low dissolved oxygen (2.5-6.0 mg L-1) in the upper 10 m of the water column. The spring upwelling increased the mixed-layer phosphate, nitrate, and silicate concentrations to roughly 1, 15, and 15 mu mol L-1, respectively, and improved the light transparency in the euphotic zone. This improvement in phytoplankton growing conditions was followed by an increase in chlorophyll-a concentrations. The summer upwelling was weaker and occurred over a smaller geographical area (122 degrees 20'-123 degrees 00' E, 31 degrees 15'-31 degrees 50' N). Strongly influenced by turbid Changjiang diluted water (CDW), it had little impact on the upper 10 m of the water column but instead increased nutrient concentrations at greater depths. The high concentration of particulates in the CDW reduced light transmission in the upper 10 m and, hence, limited phytoplankton growth throughout the water column. Chlorophyll-a concentrations in the summer upwelling area were roughly an order of magnitude lower than in the spring. Water clarity, as influenced by the CDW, appears to be the principal factor limiting the impact of upwelling on phytoplankton biomass in this area.

Nutrients in the Changjiang River

N, P and SiO3-Si in the Changjiang mainstream and its major tributaries and lakes were investigated in the dry season from November to December, 1997, and in the flood season in August and October, 1998. An even distribution of SiO3-Si was found along the Changjiang River. However, the concentrations of total nitrogen, total dissolved nitrogen, dissolved inorganic nitrogen, nitrate and total phosphorus, total particulate phosphorus increased notably in the upper reaches, which reflected an increasing impact from human activities. Those concentrations in the middle and lower reaches of the Changjiang River were relatively constant. Dissolved N was the major form of N and the particulate P was the major form of P in the Changjiang River. The molar ratio of dissolved N to dissolved P was extremely high (192.5-317.5), while that of the particulate form was low (5.6-37.7). High N/P ratio reflected a significant input of anthropogenic N such as N from precipitation and N lost from water and soil etc. Dissolved N and P was in a quasi-equilibrium state in the process from precipitate to the river. In the turbid river water, light limitation, rather than P limitation, seemed more likely to be a controlling factor for the growth of phytoplankton. A positive linear correlationship between the concentration of dissolved N and the river's runoff was found, mainly in the upper reaches, which was related to the non-point sources of N. Over the past decades, N concentration has greatly increased, but the change of P concentration was not as significant as N. The nutrient fluxes of the Changjiang mainstream and tributaries were estimated, and the result showed that the nutrient fluxes were mainly controlled by the runoff, of which more than a half came from the tributaries. These investigations carried out before water storage of the Three Gorges Dam will supply a scientific base for studying the influences of the Three Gorges Dam on the ecology and environment of the Changjiang River and its estuary.

Seasonal changes in the distribution of dissolved organic nitrogen in coastal and open-ocean waters in the North East Pacific: sources and sinks

The distribution of dissolved organic nitrogen (DON) and nitrate were determined seasonally (winter, spring and summer) during three years along line P, i.e. an E-W transect from the coast of British Columbia, Canada, to Station P (50degreesN, 145degreesW) in the subarctic North East Pacific Ocean. In conjunction, DON measurements were made in the Straits of Juan de Fuca and Georgia within an estuarine system connected to the NE Pacific Ocean. The distribution of DON at the surface showed higher values of 4-17 muM in the Straits relative to values of 4-10 muM encountered along line P, respectively. Along line P, the concentration of DON showed an inshore-offshore gradient at the surface with higher values near the coast. The equation for the conservation of DON showed that horizontal transport of DON (inshore-offshore) was much larger than vertical physical mixing. Horizontal advection of DON-rich waters from the coastal estuarine system to the NE Pacific Ocean was likely the cause of the inshore-offshore gradient in the concentration of DON. Although the concentration of DON was very variable in space and time, it increased from winter to summer, with an average build up of 4.3 muM in the Straits and 0.7 muM in the NE subarctic Pacific. This implied seasonal DON sources of 0.3 mmol N m(-2) d(-1) at Station P and 1.5 mmol N m(-2) d(-1) in the Straits, respectively. These seasonal DON accumulation rates corresponded to about 15-20% of the seasonal nitrate uptake and suggested that there was a small seasonal build up of labile DON at the surface. However, the long residence times of 180-1560 d indicated that the most of the DON pool in surface waters was refractory in two very different productivity regimes of the NE Pacific. (C) 2002 Elsevier Science Ltd. All rights reserved.

Nitrogen isotopic fractionation during a simulated diatom spring bloom: importance of N-starvation in controlling fractionation

N isotope fractionation (epsilon) was first determined during ambient NO3- depletion in a simulated diatom spring bloom. After 48 h of N-starvation, NH4+ was resupplied to the diatoms in small pulses to simulate grazer-produced N and then epsilon was determined. Large variations in epsilon values were observed: from 2.0-3.6 to 14-0 parts per thousand during NO3- and NH4+ uptake, respectively. This is the first study reporting an epsilon value as low as 0 to 2 parts per thousand for NH4+ uptake and we suggest that greater N demand after N-starvation may have drastically reduced NH3 efflux out of the cells. Thus the N status of the phytoplankton and not the ambient NH4+ concentration may be the important factor controlling epsilon, because, when N-starvation increased, epsilon values for NH4+ uptake decreased within 30 h. This study may thus have important implications for interpreting the delta(15)N of particulate N in nutrient-depleted regimes in temperate coastal oceans.

Nitrogen isotope fractionation during nitrate, ammonium and urea uptake by marine diatoms and coccolithophores under various conditions of N availability

Stable isotopes of N provide a new approach to the study of algal production in the ocean, yet knowledge of the isotope fractionation (epsilon) in various oceanic regimes is lacking. Here we report large and rapid changes in isotope composition (delta(15)N) of 2 coastal diatoms and 2 clones (open and coastal) of a coccolithophore grown in the simultaneous presence of nitrate, ammonium and urea under varying conditions of N availability (i.e. N-sufficiency and N-starvation followed by N-resupply) and hence different physiological states, During N-sufficiency, the delta(15)N of particulate organic N (PON) was well reproduced, using a model derived from Rayleigh distillation theory, with constant epsilon similar to that for growth on each individual N source. However, following N-resupply, the variations in delta(15)N(PON) could be well explained only in the case of the open ocean Emiliania huxleyi, with epsilon similar to N-sufficient conditions. It was concluded that the mechanism of isotope fractionation changed rapidly with N availability for the 3 coastal clones. However, in the case of E. huxleyi isolated from the Subarctic Pacific Ocean, no evidence of a change in mechanism was found, suggesting that perhaps open ocean species can quickly recover from N-depleted conditions.

Size-fractionated phytoplankton biomass in autumn of the Changjiang (Yangtze) River Estuary and its adjacent waters after the Three Gorges Dam construction

A cruise was undertaken from 3rd to 8th November 2004 in Changjiang (Yangtze) River Estuary and its adjacent waters to investigate the spatial biomass distribution and size composition of phytoplankton. Chlorophyll-a (Chl-a) concentration ranged 0.42-1.17 mu g L-1 and 0.41-10.43 mu g L-1 inside and outside the river mouth, with the mean value 0.73 mu g L-1 and 1.86 mu g L-1, respectively. Compared with the Chl-a concentration in summer of 2004, the mean value was much lower inside, and a little higher outside the river mouth. The maximal Chl-a was 10.43 mu g L-1 at station 18 (122.67 degrees E, 31.25 degrees N), and the region of high Chl-a concentration was observed in the central survey area between 122.5 degrees E and 123.0 degrees E. In the stations located east of 122.5 degrees E, Chl-a concentration was generally high in the upper layers above 5 m due to water stratification. In the survey area, the average Chl-a in sizes of > 20 mu m and < 20 mu m was 0.28 mu g L-1 and 1.40 mu g L-1, respectively. High Chl-a concentration of < 20 mu m size-fraction indicated that the nanophytoplankton and picophytoplankton contributed the most to the biomass of phytoplankton. Skeletonema costatum, Prorocentrum micans and Scrippsiella trochoidea were the dominant species in surface water. The spatial distribution of cell abundance of phytoplankton was patchy and did not agree well with that of Chl-a, as the cell abundance could not distinguish the differences in shape and size of phytoplankton cells. Nitrate and silicate behaved conservatively, but the former could probably be the limitation factor to algal biomass at offshore stations. The distribution of phosphate scattered considerably, and its relation to the phytoplankton biomass was complicated.

The status and characteristics of eutrophication in the Yangtze River (Changjiang) estuary and the adjacent East China Sea, China

Eutrophication has become increasingly serious and noxious algal blooms have been of more frequent occurrence in the Yangtze River Estuary and in the adjacent East China Sea. In 2003 and 2004, four cruises were undertaken in three zones in the estuary and in the adjacent sea to investigate nitrate (NO3-N), ammonium (NH4-N), nitrite (NO2-N), soluble reactive phosphorus (SRP), dissolved reactive silica (DRSi), dissolved oxygen (DO), phytoplankton chlorophyll a (Chl a) and suspended particulate matter (SPM). The highest concentrations of DIN (NO3-N+NH4-N+NO2-N), SRP and DRSi were 131.6, 1.2 and 155.6 mu M, respectively. The maximum Chl a concentration was 19.5 mg m(-3) in spring. An analysis of historical and recent data revealed that in the last 40 years, nitrate and SRP concentrations increased from 11 to 97 mu M and from 0.4 to 0.95 mu M, respectively. From 1963 to 2004, N:P ratios also increased from 30-40 up to 150. In parallel with the N and P enrichment, a significant increase of Chl a was detected, Chl a maximum being 20 mg m(-3), nearly four times higher than in the 1980s. In 2004, the mean DO concentration in bottom waters was 4.35 mg l(-1), much lower than in the 1980s. In comparison with other estuaries, the Yangtze River Estuary was characterized by high DIN and DRSi concentrations, with low SRP concentrations. Despite the higher nutrient concentrations, Chl a concentrations were lower in the inner estuary (Zones 1 and 2) than in the adjacent sea (Zone 3). Based on nutrient availability, SPM and hydrodynamics, we assumed that in Zones 1 and 2 phytoplankton growth was suppressed by high turbidity, large tidal amplitude and short residence time. Furthermore, in Zone 3 water stratification was also an important factor that resulted in a greater phytoplankton biomass and lower DO concentrations. Due to hydrodynamics and turbidity, the open sea was unexpectedly more sensitive to nutrient enrichment and related eutrophication processes.

Long-term ecological interactions between nutrient and phytoplankton community in the Changjiang estuary

Both nitrate (NO (3) (-) ) and soluble reactive phosphate (PO (4) (3-) ) concentration in the freshwater end-member at the mouth of the Changjiang River have increased dramatically since the 1960s. Within the same period in the sea area, with surface salinity > 30, NO (3) (-) concentration has shown an obvious increase, PO (4) (3-) has not changed greatly and dissolved reactive silica (SiO (3) (2-) ) has deceased dramatically. An examination of the elemental ratio of NO (3) (-) to PO (4) (3-) at the mouth of the Changjiang River did not show a systematic trend from the 1960s to 2000s largely because both nutrients increased simultaneously. In comparison, the elemental ratio of dissolved inorganic nitrogen (DIN) to PO (4) (3-) in surface seawater, with salinity > 22, has shown a clearly increasing trend. Furthermore, an overall historical change of the SiO (3) (2-) :PO (4) (3-) ratio has undergone a reverse trend in this area. Based on the changes of SiO (3) (2-) :PO (4) (3-) and DIN:PO (4) (3-) ratios, we can conclude that an overall historical change of SiO (3) (2-) :DIN ratio has decreased in this area from the 1950-1960s to 2000s. The argument that phytoplankton productivity in the Changjiang estuary has been enhanced by increasing nutrient input from the riverine transport was supported by these results. A comparative study analyzing the shift of phytoplankton composition from the mid-1980s to 2000s was also made. The results indicated that the average yearly percentage of diatom species in the Changjiang estuary has decreased from 84.6% during 1985-1986 to 69.8% during 2004-2005. Furthermore, the average yearly percentage of diatom abundance in the Changjiang estuary decreased from 99.5% during to 75.5% over the same time period, while the abundance of dinoflagellates has increased dramatically, from 0.7% to 25.4%.

Biosorption of copper(II) from aqueous solutions by green alga Cladophora fascicularis

Biosorption is an effective means of removal of heavy metals from wastewater. In this work the biosorption behavior of Cladophora fascicularis was investigated as a function of pH, amount of biosorbent, initial Cu2+ concentration, temperature, and co-existing ions. Adsorption equilibria were well described by Langmuir isotherm models. The enthalpy change for the biosorption process was found to be 6.86 kJ mol(-1) by use of the Langmuir constant b. The biosorption process was found to be rapid in the first 30 min. The presence of co-existing cations such as Na+, K+, Mg2+, and Ca2+ and anions such as chloride, nitrate, sulfate, and acetate did not significantly affect uptake of Cu2+ whereas EDTA substantially affected adsorption of the metal. When experiments were performed with different desorbents the results indicated that EDTA was an efficient desorbent for the recovery of Cu2+ from biomass. IR spectral analysis suggested amido or hydroxy, C=O, and C-O could combine strongly with Cu2+.

Preparation of Dendritic Copper Nanostructures and Their Characterization for Electroreduction

Dendritic copper nanostructures of different morphologies were synthesized by a surfactant-free electrochemical method. Single crystal nature of the nanostructures was revealed from their X-ray diffraction and electron diffraction patterns. Mechanism of dendrite formation was discussed from thermodynamic aspects using the concept of supersaturation. Supersaturation of the copper metal reduced on the surface of the electrode was the crucial factor for the generation of different morphologies. Effects of applied potential, temperature, and the solution concentration on the supersaturation were studied. The NO3- and H2O2 electroreduction ability of the dendritic materials was tested. Use of copper dendrite-modified electrode as NO3- sensor was demonstrated.