On the possible role of organic melanoidin polymers as matrices for prebiotic activity

Summary One of the major diagenetic pathways of organic matter in recent sediments involves the condensation of cellular constituents, particularly amino acids and sugars, into insoluble melanoidin-type polymers. These polymers consist mainly of humic and fulvic acids and make up the major part of the organic carbon reservoir in recent sediments. We suggest that a similar set of reactions between abiotically formed amino acids and sugars, and more generally between aldehydes and amines, occurred on a large scale in the prebiotic hydrosphere. The rapid formation of this insoluble polymeric material would have removed the bulk of the dissolved organic carbon from the primitive oceans and would thus have prevented the formation of an "organic soup".Melanoidin polymers have several properties which make them attractive hypothetical precursors of contemporary oxidation-reduction coenzymes: 1. they contain heterocyclic nitrogen compounds similar to the nitrogenous bases; 2. they contain a high concentration of stable free radicals; and 3. they tend to concentrate those heavy metals which play prominent roles in contemporary enzymic redox processes. The prebiotic formation of similar polymers could, therefore, have provided the starting point for a basic class of biochemical reactions.We suggest that the prebiotic scenario involved chemical and protoenzymic reactions at the sediment-ocean interface in relatively shallow waters and under conditions not much different from those of the recent environment.On leave from the Isotope Department, Weizmann Institute of Sciences, Rehovot, Israel. This is the address for reprint requests.On leave from the Department of Cell and Molecular Biology, San Francisco State University, San Francisco, California.On leave from the Department of Biophysics, University of Houston, Houston, Texas.     

Determination of Trace Element Stability in Sediments Using Redox Gel Probes: Probe Construction and Theoretical Performance

A simple and inexpensive technique is described that can be used to assess the stability of redox-sensitive compounds in the sediments of wetlands and other shallow water environments. In this method, solid redox-sensitive compounds, such as manganese dioxide (MnO 2 ), are incorporated into agar gels held in rigid plastic holders. One surface of the gel remains exposed along the length of the resulting probe. The probes are pushed vertically into sediments and are left in situ for a period of time (days to weeks), after which they are visually inspected and chemically analyzed. The diffusion of nonreactive solutes (e.g., sulfate) in 2% (wt/vol) agar was unaffected by the presence of immobilized MnO 2 particles. The rate of dissolution of particulate MnO 2 in agar gels in the presence of an external diffusing reductant (L-ascorbic acid) could be quantified by digital analysis of pixel density on gel images. Redox gel probes incubated in the sediment of a wetland built to remove manganese from circumneutral pH coal mine drainage demonstrated different patterns of depth-dependent MnO 2 stability along a 15-m transect. MnO 2 gel probe results were consistent with data obtained using sediment cores and porewater diffusion samplers.     

Pollution characteristics of mercury (Hg) in surface sediments of major basins,China

To investigate the pollution status and potential pollution risk of mercury (Hg) in China, surface sediment samples were collected from eight hundred and eighty-one sites, including ten major basins (Songhua River Basin (SRB), Liao River Basin (LRB), Hai River Basin (HRB), Yellow River Basin (YRB), Huai River Basin (HuRB), Yangtze River Basin (YtRB), Pearl River Basin (PRB), Southeastern River Basin (SeRB), Southwestern River Basin (SwRB) and Northwestern River Basin (NwRB)). Results showed that Hg concentrations in sediments of ten basins in China ranged from 0.001 to 8.800 mg/kg, with average ± S.D. value of 0.274 ± 0.675 mg/kg, which was obviously higher than Chinese soil background value (0.038 mg/kg) and Chinese sediment background value (0.040 mg/kg). The mean Hg concentration of ten basins decreased in the order of HRB > YtRB > SRB > PRB > HuRB > SwRB > YRB > SeRB > LRB > NwRB. Moreover, it was found that the Hg concentrations in the sediments of LRB, YtRB, PRB, SeRB and SwRB were partly driven by their total organic carbon (TOC) contents, while the effect of pH on the distribution of Hg was not obvious. The Hg concentration data were also compared with those got in other periods (1994–2015) to obtain the general variation tendency of Hg level. It was recorded that Hg concentrations in HRB have remained on high levels for a long history, while Hg contamination situation in YRB after 2004 has potentially turned to be better. The results of pollution assessment by sediment quality assessment guidelines (SQGs), contamination factor (CF), geoaccumulation index (I_geo) and potential ecological risk (E_i) suggested that YRB and HRB were the most seriously polluted river basins among the ten basins. It is urgent of constructing SQGs in China to scientifically evaluate the Hg pollution in the future.     

Modelling production and biomasses of zoobenthos in lakes

This work presents a dynamic model to predict zoobenthos in lakes. The model has been developed within the framework of a more comprehensive lake ecosystem model, LakeWeb, which also accounts for the following functional groups of organisms, phytoplankton, bacterioplankton, two types of zooplankton (herbivorous and predatory), macrophytes, prey fish and predatory fish. This work also presents a new data-base for zoobenthos in lakes. Many of the lakes included in this study are situated in the former Soviet Union. They were investigated during the Soviet period and those results have been largely unknown in the West. Using this data-base, this work also presents new empirical models for zoobenthos. The new dynamic model gives seasonal variations (the calculation time, dt, is 1 week using Euler's method and enough iterations to get stable solutions). The basic aim of the dynamic model is that it should capture general functional and structural patterns in lakes. We have demonstrated by several model tests along limnological gradients (total phosphorus concentrations, pH, lake colour, latitude and lake size) that the dynamic model gives predictions that agree well with the values given by the empirical regressions, and also expected and requested divergences from these regressions when they do not provide sufficient resolution. It would have been very difficult indeed to carry out such tests regarding ecosystem responses using traditional methods with extensive field studies in a few lakes. We have given algorithms for (1) production of zoobenthos from eating macrophytes, benthic algae and sediments, (2) elimination (related to the turnover time of zooplankton), and (3) zoobenthos consumption by prey fish, and the factors influencing these processes/rates. The model is driven by data easily accessed from standard monitoring programs or maps a prerequisite for practical utility in contexts of lake management.     

Contamination of a dredged material disposal site La Rochelle Bay,France .The use of the acetylcholinesterase activity of Mytilus edulis L. as a biomarker of pesticides: the need for a critical approach

A single aspect of the toxic impact of a dredged material disposal site located near a mussel-farming zone was followed for eight months. Acetylcholinesterase activity (AChE) of Mytilus edulis was investigated as a biomarker for possible contamination by neurotoxic compounds (carbamates and/or organophosphorous pesticides). Our observations showed that the enzymatic activities (including AChE) of these harbour mussels were decreased in sites directly and indirectly influenced (according to hydrodynamic conditions) by the dumping of dredged sediments, suggesting possible contamination by pesticides. The strong correlations observed between AChE activity and growth parameters (length and weight) seems to show, however, that the enzyme activity is also indirectly controlled through growth restriction, which may imply limitation of the development of the nervous system in juveniles. The concentration of total proteins, as well as the spawning process also seem to disturb the assessment of AChE activity. These field observations clearly indicate that the use of this enzyme activity as a biomarker should proceed with caution. For example, the seasonal variability of such activity should be taken into account in a biomonitoring programme.     

Stimulation of sulfate reduction rates in Mediterranean fish farm sediments inhabited by the seagrass <Emphasis Type="Italic">Posidonia oceanica</Emphasis>

Sulfate reduction rates and biogeochemical parameters of fish farm sediments across the Mediterranean were investigated in the order to evaluate the potential effects of organic matter inputs on habitat quality for the common seagrass Posidonia oceanica. Four study sites were selected in Spain, Italy, Greece and Cyprus to represent the Mediterranean basin. P. oceanica was found in immediate vicinity of all the farms, which were located at physically exposed sites about 1 km from the shore lines. Organic matter accumulation, sulfate reduction rates and sulfur pools were measured in depth profiles along transects from the farms in both bare and vegetated sediments. Results show that although the organic matter accumulation was minor at the sites (POC < 2.8% DW), the sulfate reduction rates were high, in particular at the largest farm in Italy (up to 212 mmol m⁻² d⁻¹), similar to rates found at shallower, temperate fish farm sites, where higher sedimentation rates can be expected. Sulfate reducing bacteria in these low-organic, carbonate-rich Mediterranean sediments respond strongly to organic matter loadings and cause habitat degradation. Sulfate reduction rates measured in the P. oceanica sediments were among the highest recorded (7.8–42.0 mmol m⁻² d⁻¹) similar to rates found in degrading meadows impacted by organic matter loadings. As sulfate reduction rates were correlated with the sedimentation rates along the transects rather than organic matter pools this suggests mineralization processes were controlled by organic matter loading in fish farm sediments. The vegetated sediments near the net cages were more reduced due to accumulation of sulfides compared to control sites, which is a possible contributing factor to the observed seagrass decline in the farm surroundings. It is recommended that Mediterranean fish farms are placed in areas with rapid dispersal of particulate waste products to minimize organic matter loading of the sediments and thereby preserve habitat quality for benthic fauna and flora.     

The extent and significance of petroleum hydrocarbon contamination in Crater Lake,Oregon

In order to evaluate hydrocarbon inputs to Crater Lake from anthropogenic and natural sources, samples of water, aerosol, surface slick and sediment were collected and analyzed by gas chromatography-mass spectrometry (GC-MS) for determination of their aliphatic and aromatic hydrocarbon concentrations and compositions. Results show that hydrocarbons originate from both natural (terrestrial plant waxes and algae) and anthropogenic (petroleum use) sources and are entering the lake through direct input and atmospheric transport. The concentrations of petroleum hydrocarbons range from low to undetectable. The distributions and abundances of n-alkanes, polycyclic aromatic hydrocarbons (PAH) and unresolved complex mixture (UCM) from petroleum are similar for all surface slick sampling sites. The estimated levels of PAH in surface slicks range from 7–9 ng/m² which are low. Transport of petroleum-derived hydrocarbons from the lake surface has resulted in their presence in some sediments, particularly near the boat operations mooring (total petroleum HC = 1440 μg/kg, dry wt. compared to naturally derived n-alkanes, 240 μg/kg, dry wt.). The presence of biomarkers such as the tricyclic terpanes, hopanes and steranes in shallow sediments further confirms petroleum input from boat traffic. In the deep lake sediments, petroleum hydrocarbon concentrations were very low (16 μg/kg, dry wt.). Very low concentrations of PAH were detected in shallow sediments (17–40 μg/kg at 5 m depth near the boat operations) and deep sediments (3–15 μg/kg at 580 m depth). The individual PAH concentrations in sediments (μg/kg or ppb range) are at least three orders of magnitude less than reported threshold effects levels (mg/kg or ppm range, test amphipod Hyalella azteca). Therefore, no adverse effects are expected to occur in benthic biota exposed to these sediments. Boating activities are leaving a detectable level of petroleum in surface waters and lake sediments but these concentrations are very low.     

An antiferromagnetically coupled trinuclear Cu(II) complex containing μ(O,O′), μ(O) carboxylates and μ(O) phenoxide bridges

The trinuclear complex [L₂Cu₃(CF₃CO₂)₄] (1) has been synthesized and its crystal structure determined. It consists of a linear arrangement of Cu(II) centers. The central copper atom is bonded to six oxygen atoms and has a tetragonally distorted octahedral geometry, while the terminal copper atoms are bonded to three oxygen and two nitrogen atoms and show a distorted square pyramidal geometry. The complex shows di-μ(O,O′) syn-syn carboxylate bridging as well as monoatomic (μ-O) bridging, along with phenolate (μ-O) oxygen bridging. Cryomagnetic investigations in the range 2-300 K revealed an antiferromagnetic spin exchange interaction with J = −95.7 cm⁻¹, based on the isotropic exchange model H_ex = −2J[S₁ · S₂ + S₂ · S₃].     

A dinuclear copper(II) complex with a Cu(O, N-O)Cu bridging core: structural and magnetic (experimental and density functional theory) studies

The molecular and electronic structure, along with the magnetic properties of a dinuclear complex in which two copper ions interact through a phenoxo oxygen atom and an oximato group are presented. The complex [CuL³Cu(O₂CCH₃)]3H₂O ·  0.5CH₃OH (3) crystallizes in the monoclinic space group Cc, with a=28.432(2) Å, b=12.305(1) Å, c=13.159(1) Å and β=99.580(9)°. The X-ray molecular structure shows that the core of the molecule comprising the two metal ions and the seven neighboring donors is nearly planar. The copper(II) ions were found to be antiferromagnetically coupled with a singlet-triplet splitting of 764(4) cm⁻¹. Density Functional Theory (DFT) showed that the magnetic orbitals are largely delocalized towards the bridging area, and an antiferromagnetic interaction in good agreement with the experimental data was computed using the Broken Symmetry (BS) formalism to obtain the energy of the singlet state.     

山西耕作土壤样品磁性空间分异及其环境意义

本文分析了山西高原土壤耕作层(0-20cm)25个样品的磁性,用GIS空间分析方法,得出土壤磁化率平面分布等值线图和空间三维模型。磁化率空间分布机理如下:首先,强烈的人为影响使土壤中磁性矿物人为来源占有重要地位。第二,土壤磁性矿物以亚铁磁性的磁铁矿和磁赤铁矿为主导。第三,土壤磁化率极值差及其与母质之间的差异均受广泛而较均一的黄土母质的影响。第四,晋西北和晋中等区域出现土壤磁化率高值区域。第五,人为作用强烈影响掩盖了气温、降水等气候因子对土壤磁化率的作用。