Quinone-hydroquinone complexes as model components of humic acids: Theoretical studies of their structure, stability and Visible-UV spectra     

J.A. Tossell 《Geochimica et cosmochimica acta》2009,73(7):2023-2033

Humic substances present a geochemically and environmentally important, yet poorly characterized, component of dissolved organic matter. In the past they have generally been described as macromolecular polymers containing many different functional groups. Recently, it has been suggested, partly on the basis of new experimental data, that such materials are rather supramolecular in nature, consisting of smaller molecular units held together by noncovalent forces such as van der Waals forces and H-bonds. A perplexing difficulty in characterizing humic acids has always been that data expected to be informative, such as their Visible-UV spectra, were sadly lacking in structure. This has usually been explained using models in which ensembles of molecules are present characterized by either long-range charge-charge interactions or random short-range donor-acceptor interactions.Structural components resembling hydroquinone:quinone donor-acceptor complexes have been postulated to explain the near-IR and visible spectra of humic acids (Del Vecchio R., and Blough N.V. (2004) On the origin of the optical properties of humic substances. Environ. Sci. 38, 3885-3891). We have calculated structures, energetics and Visible-UV spectra for several different quinone and hydroquinone monomers and for donor-acceptor complexes formed between hydroquinone, H₂Q, the donor, and quinone, Q, the acceptor. Most of the Visible-UV spectral calculations are carried out using time-dependent density functional theory. For the monomers the calculated energies are in good agreement with experiment. We confirm that the absorption spectra of the D:A complexes have maxima at much lower energy than their monomeric components. These absorption energies are influenced by substituents on the aromatic rings, but are also sensitive functions of the distances between the aromatic rings. The importance of D:A complexes in generating a spectrum like that of natural humic acids is consistent with the model of Del Vecchio and Blough (2004). However, our calculations of reaction free energies indicate that the donor-acceptor interactions do not arise from free D:A complexes, but rather from forced or random close approach of D and A rings.  相似文献   

Spatial characterisation of the Benguela ecosystem for ecosystem-based management     

SP Kirkman  L Blamey  T Lamont  G Bianchi  JA Huggett 《African Journal of Marine Science》2016,38(1):7-22

The three countries of the Benguela Current Large Marine Ecosystem (BCLME), namely Angola, Namibia and South Africa, have committed to implementing ecosystem-based management (EBM) including an ecosystem approach to fisheries (EAF) in the region, to put in practice the principles of sustainable development in ocean-related matters. There is also recognition of the need for marine spatial planning (MSP) as a process for informing EBM with regard to the allocation and siting of ocean uses so that ecosystem health is ensured and trade-offs between ecosystem services are appropriately dealt with. Marine spatial planning is both an integrated and an area-based process, and this paper produces a spatial characterisation of the BCLME for achieving a common basis for MSP in the region, focusing on the oceanography, biology and fisheries. Recognising spatial variation in physical driving forces, primary and secondary production, trophic structures and species richness, four different subsystems are characterised: (1) north of the Angola–Benguela Front, (2) from the Angola–Benguela Front to Lüderitz, (3) from Lüderitz to Cape Agulhas, and (4) from Cape Agulhas to Port Alfred on the south-east coast of South Africa. Research and monitoring requirements of relevance for MSP and EBM in the region are identified, focusing on understanding variability and change, including with regard to the boundary areas identified for the system. To this end, 14 cross-shelf monitoring transects are proposed (including seven that are already being monitored) to estimate fluxes of biota, energy and materials within and between the subsystems. The usefulness of models for understanding ecosystem variability and changes is recognised and the need for fine-scale resolution of both sampling and modelling for adequate MSP as input to EBM for the often-conflicting interests of conserving biodiversity, and managing fisheries, recreation, offshore oil and gas exploration and exploitation, offshore mining and shipping routes, is emphasised.  相似文献   

Use of probiotic bacteria to improve growth and survivability of farmed New Zealand abalone (Haliotis iris)     

JA Hadi  AC Alfaro  RD Roberts 《新西兰海洋与淡水研究杂志》2014,48(3):405-415

The effects of two probiotic feeds containing two and three bacterial isolates were evaluated on the growth performance of New Zealand abalone (Haliotis iris). Probiotic bacteria were isolated from the guts of healthy adult abalone. The isolates were screened qualitatively and quantitatively according to their ability to hydrolyse nutrients (i.e. proteins, starch and alginate), produce acid and resist bile salts. Based on the screening results, we developed a multi-strain conglomerate of 2- and 3- probiotic bacterial strains that were supplemented into a commercial abalone feed to use in our experiments. The 2-probiotic conglomerate consisted of Exiguobacterium JHEb1 and Vibrio JH1, and the 3-probiotic conglomerate consisted of Exiguobacterium JHEb1, Vibrio JH1 and Enterococcus JHLDc. The probiotic feeding trial involved abalone juveniles (20–30 mm in maximum shell length). Both probiotic feeds significantly improved abalone growth compared to that of the unsupplemented feed. The 3-probiotic supplemented feed produced a significant shell length increase of 20.9%, a wet weight gain of 19.8% and a five-fold reduction in mortality compared to the controls. The 2-probiotic supplemented feed resulted in significant increases in shell length (15.4%) and reduced mortality (five-fold), but not in weight gain, compared to controls.  相似文献   

Effect of size grading on the growth performance of shortfin eel (Anguilla australis) during its yellow stage     

JA Hirt-Chabbert  A Sabetian  OA Young 《新西兰海洋与淡水研究杂志》2014,48(3):385-393

It is generally believed that size grading in a fish farm improves the total biomass output, because it will minimise the stress imposed by larger individuals over small individuals, resulting in higher feed intake and growth rate. The objective of this study was to evaluate the effect of size grading on individual growth performance of yellow New Zealand shortfin eel (Anguilla australis). A 109 day trial was conducted in a recirculation aquaculture system (RAS) with 103 eels of similar initial weight (101 ± 12 g). All eels were individually marked by PIT (passive integrated transponder) tags. On day 42, eels were graded to establish the following groups: only small eels (S-graded ≤ 135 g), only large eels (L-graded > 135 g), and small and large eels together (S-ungraded and L-ungraded). The large eels showed better specific growth rate (SGR), feed intake (FI) and feed conversion ratio (FCR) than the small eels. Nevertheless, no significant differences were found either between L-graded and L-ungraded or between S-graded and S-ungraded. The age of eels was not significantly different between groups. These findings suggest that the individual growth rate performance of the eels is not primarily a consequence of social interaction among tank-mates.  相似文献   

块系岩体间黏弹性性质对摆型波传播的影响     

王凯兴  潘一山  曾祥华  肖永惠  李忠华  贾宝新 《岩土力学》2013,34(Z2):174-179

基于深部非连续自应力等级块系岩体构造理论,研究冲击载荷在块系岩体中以摆型波形式传播时岩块间黏弹性性质对摆型波传播的影响。当岩块间具有五种不同黏弹性性质时,通过对块系岩体的始端和末端区域中间岩块加速度响应计算及各岩块加速度正负摆幅幅值分析可知：岩块间黏性变化时,对岩块加速度衰减周期没有影响,但黏性增大时各岩块正负摆幅下降幅度比黏性周期增大时大;岩块间弹性变化时岩块加速度衰减周期均发生变化,但弹性减小时正负摆幅值向平衡位置平移,弹性周期减小时块系岩体的前半部分岩块正负摆幅曲线均出现波动且负摆波动较大,岩块间弹性梯级增大时,岩块加速度迅速衰减,同时各岩块加速度的正负摆幅曲线在初始端区域出现波动。  相似文献   

Pyrite,marcasite, and arsenopyrite type minerals: Crystal chemical and structural principles   总被引：1，自引：0，他引：1  

J. A. Tossell  D. J. Vaughan  J. K. Burdett 《Physics and Chemistry of Minerals》1981,7(4):177-184

Quantitative molecular orbital (MO) calculations and qualitative perturbational MO arguments are used to interpret the spectra and structure of transition metal dichalcogenides and related compounds. Competition between pyrite (FeS₂), marcasite (FeS₂) and loellingite (FeAs₂) structure types is explained in terms of the number of electrons occupying a set of MO's obtained from the mixing of dianion (A ₂) orbitals and metal (M) dσ orbitals. Direct metal-metal d orbital interaction is argued to be small. Attention is focused upon the M - A - M angles which differ substantially among the three structure types as a consequence of varying numbers of electrons in orbitals which closely resemble the pπ* orbitals of the dianions. Variations in M - A and A - A distances can also be understood in terms of the occupations of this set of MO's. Disulfide valence region photo-emission spectra are interpreted in terms of calculations on MS₆ and S₆ molecular clusters. M3d orbitals are found to progressively approach the S3p orbitals with increasing atomic number of M from Fe to Ni. For CuS₂ comparison of calculation and experiment supports an approximate electron configuration of Cu⁺¹ S ₂ ^?1 .  相似文献   

Interpretation of the auger electron spectra (AES) of sulfide minerals     

David J. Vaughan  John A. Tossell 《Physics and Chemistry of Minerals》1986,13(5):347-350

Auger electron spectra (AES) of sulfides are interpreted using published photoelectron spectra, sulfurK _β X-ray emission spectra (XES) and Multiple ScatteringX _α calculations on metal-sulfide molecular clusters and using newly measured spectra for ZnS, Cu₂S and MoS₂. For compounds without appreciable metald-sulfur 3p interactions, only one sulfur LVV peak or a closely spaced doublet is observed. For those with substantial metald-sulfur 3p interactions additional peaks occur, with peaks at lower electron kinetic energy arising from ejection of electrons from orbitals more tightly bound than theS3p, and those with higher kinetic energy arising from electrons in less tightly bound orbitals. Thus, for many sulfide minerals, the sulfur LVV Auger Spectrum is essentially a self-convolution of the valence band density of states weighted by the amount of S3p character, and can be predicted from a knowledge of the sulfurK _β X-ray emission spectra and the X-ray photoelectron spectra.  相似文献   

Correlation of 29Si nuclear magnetic resonance chemical shifts in silicates with orbital energy differences obtained from X-ray spectra     

J. A. Tossell 《Physics and Chemistry of Minerals》1984,10(3):137-141

Trends in ²⁹Si nuclear magnetic resonance (NMR) chemical shifts in silicates are shown to arise primarily from changes in the paramagnetic contribution to the shift, σ^para. Using the average excitation energy approximation, changes in σ^para may be correlated with changes in the separation of high energy occupied and low energy unoccupied molecular orbitals. The required molecular orbital (MO) energy differences may be obtained from x-ray emission and absorption spectra. Shifts in σ to high field as silicate polymerization increases are associated with increased occupied to unoccupied MO energy differences. Substitution of Al for Si (and consequent introduction of electropositive cations, such as Na) reduces the occupied to unoccupied orbital energy gap causing shifts of σ to low field. The observed correlation indicates that ²⁹Si NMR is capable of giving information on silicate electronic structure.  相似文献   

NDCI法Ⅱ类水体叶绿素a浓度高光谱遥感数据估算   总被引：1，自引：0，他引：1  

安如  刘影影  曲春梅  Quaye-BallardJA  梁欣  徐晓峰  王喆  姜丹萍 《湖泊科学》2013,25(3):437-444

以太湖、巢湖为研究区,以Hyperion和HJ-1A卫星HSI高光谱数据以及实测水质浓度数据为实验数据,引入归一化叶绿素指数(NDCI),对Ⅱ类水体的高光谱叶绿素a浓度估算进行分析研究.首先对高光谱数据的光谱通道设置以及水体光谱特征进行分析,研究确定模型的最优波段.然后,将确定最优波段后的NDCI反射率因子作为变量与实测样本点数据进行回归分析,得到NDCI与叶绿素a浓度之间的回归关系,进行叶绿素a浓度的估算.与常用的比值法、一阶微分法和三波段法相比,NDCI的性能优于这3种方法,表明NDCI是一种计算简单、估算精度高、实用性强的Ⅱ类水体叶绿素a浓度估算方法.  相似文献   

Estimating periphyton standing crop in streams: a comparison of chlorophyll a sampling and visual assessments     

C Kilroy  DJ Booker  L Drummond  JA Wech  TH Snelder 《新西兰海洋与淡水研究杂志》2013,47(2):208-224

Periphyton standing crop is often measured as chlorophyll a but there is increasing interest in using visual assessments of periphyton cover. Visual methods are rapid and require no sample analysis, but can be regarded as subjective with high inter-operator variability. We investigated variability in periphyton standing crop across operators, rivers and time, as determined visually and from chlorophyll a measurements. We found that visual assessments (comprising percentage cover estimates of up to eight periphyton categories) distinguished sites and occasions as effectively as chlorophyll a. Furthermore, an estimate of chlorophyll a could be derived from the visual assessments. Because our surveys were conducted in only three rivers, general applicability of the derivation of estimated chlorophyll a from the visual assessments warrants further investigation. The current recommendation of 20 views was sufficient for realistic visual assessments of average cover. Overall, our results indicated that inter-operator variability in visual assessments need not be a major concern, given adequate training.  相似文献