The isotopic cycle of oceanic phosphate,I

Steady-state conditions seem to exist in the Atlantic and Pacific Oceans in the case of the¹⁸O content of dissolved phosphate. The measured δ¹⁸O(PO₄^3?) values are fairly constant at all latitudes and depths. A constant difference of about 1‰ exists between average Atlantic and Pacific results. Oxygen isotope measurements carried out on phosphate in the organic matter of fish, showed an average difference of about 3‰ when compared with dissolved oceanic phosphate. Such a difference can be attributed to biological fractionation effects in the metabolism of phosphate. However, the equilibrium fractionation factors in the phosphate-water system are poorly known and consequently we do not know whether this difference represents an approach to, or a deviation from, isotopic equilibrium conditions.     

Calcium and phosphate in the Jordan Gulf of Aqaba

Water and sediment samples taken from near the Port of Aqaba have been examined for calcium and phosphate in order to determine the effect of phosphate rock dust on the Jordan Gulf of Aqaba. Normal values for calcium and phosphate were found except near the town's sewage outlet where the phosphate was relatively higher.     

The quality of “old” oceanographic phosphate data

Temporal trends of substances in the environment can only be proved if the old and the new data are reliable. For the quantitative chemical analysis of inorganic phosphate in sea water the historical development during the past hundred years is reviewed briefly. A critical examination of the different methods shows that phosphate data can be considered reliable from 1923 onwards, if a number of analytical conditions were fulfilled.     

Enhanced attenuation of septic system phosphate in noncalcareous sediments

Review of phosphate behavior in four mature septic system plumes on similar textured sand has revealed a strong correlation between carbonate mineral content and phosphate concentrations. A plume on calcareous sand (Cambridge site, 27 wt % CaCO3 equiv.) has proximal zone PO4 concentrations (4.8 mg/L P average) that are about 75% of the septic tank effluent value, whereas three plumes on noncalcareous sand (Muskoka, L. Joseph, and Nobel sites, <1 wt % CaCO3 equiv.) have proximal zone phosphate concentrations (<0.1 mg/L P) that are consistently less than 2% of the effluent values. Phosphate attenuation at the noncalcareous sites appears to be an indirect result of the development of acidic conditions (site average pH 3.5 to 5.9) and elevated Al concentrations (up to 24 mg/L), which subsequently causes the precipitation of Al-P minerals such as variscite (AlPO4 x 2H2O). This is supported by scanning electron microscope analyses, which show the widespread occurrence of (Al+P)--rich secondary mineral coatings on sand grains below the infiltration beds. All of these septic systems are more than 10 years old, indicating that these attenuation reactions have substantial longevity. A field lysimeter experiment demonstrated that this reaction sequence can be readily incorporated into engineered waste water treatment systems. We feel this important P removal mechanism has not been adequately recognized, particularly for its potential significance in reducing P loading from septic systems in lakeshore environments.     

Excess protactinium in phosphate nodules from a coastal upwelling zone

Measurements of²³¹Pa/²³⁵U and²³⁰Th/²³⁴U activity ratios have been made for a suite of Quaternary age phosphate nodules from the upwelling zone off Peru and Chile. Many of these samples contain more²³¹Pa than would be predicted based on closed-system²³⁰Th/²³⁴U ages unlike samples from non-upwelling environments which have been shown to have concordant²³¹Pa and²³⁰Th ages. Peru/Chile phosphate nodules apparently pick up²³¹Pa preferentially to²³⁰Th. This is most likely a result of prior fractionation of protactinium and thorium in the open ocean. Highly productive coastal upwelling zones may be added to the growing list of localities where fractionation between thorium and protactinium isotopes has been observed in marine sediments.     

Characteristics of phosphate adsorption onto granulated coal ash in seawater

The deterioration of sediments is a serious environmental problem. Controlling nutrient release fluxes from sediments is important to alleviating eutrophication and to reducing terrigenous nutrient loads. The purpose of this study was to evaluate the phosphate removal performance of granulated coal ash (GCA) from seawater, which is produced from coal thermal electric power generation. Batch experiments were carried out to investigate the removal kinetics of phosphate from seawater under both oxic and anoxic conditions. Phosphate was removed well from seawater under both oxic and anoxic conditions. The adsorption isotherm for phosphate revealed that GCA could remove phosphate effectively from seawater above a concentration of 1.7 μmol L⁻¹. GCA can reduce the concentration of phosphate in seawater effectively under anoxic conditions where iron type adsorbents cannot be applied. Therefore, GCA could potentially be used to adsorb phosphate in the organically-enriched sediment, which generally occurs under highly reductive conditions.     

Oxygen isotope measurements of phosphate from fish teeth and bones

In situ measurements of lunar surface brightness temperatures made as a part of the Apollo Lunar Surface Experiments Package at the Apollo 15 Hadley Rille landing site are reported. Data derived from 5 thermocouples of the Heat Flow Experiment, which are lying on or just above the surface, are used to examine the thermal properties of the upper 15 cm of the lunar regolith using eclipse and nighttime cool-down temperatures. Application of finite-difference techniques in modeling the lunar soil shows the thermocouple data are best fit by a model consisting of a low-density and low-thermal conductivity surface layer approximately 2 cm thick overlying a region increasing in conductivity and density with depth. Conductivities on the order of 1 × 10^?5 W/cm-°K are postulated for the upper layer, with conductivity increasing to the order of 1 × 10^?4 W/cm-°K at depths exceeding 20 cm. An increase in mean temperature with depth indicates that the ratio of radiative to conductive transfer at 350°K is 2.7 for at least the upper few centimeters of lunar soil; this value is nearly twice that measured for returned lunar fines. The thermal properties model deduced from Apollo 15 surface temperatures is consistent with earth-based microwave observations if electrical properties measured on returned lunar fines are assumed.     

鄱阳湖氮磷营养盐变化特征及潜在性富营养化评价

根据2008-10至2009-07之间4次的记录资料,阐述了鄱阳湖区氮磷营养盐的时间以及空间变化特征,并对硝氮、氨氮、磷酸盐和pH进行了相关分析,对鄱阳湖区进行了潜在性富营养化评价.结果表明:该湖区氮磷营养盐随时间和空间的不同呈现不同的变化规律,湖区水质受河流径流以及浮游植物的影响较大.在时间分布上表现出4月份的N/P比值最小,说明该季节正是浮游植物生长和繁殖最主要时期.在空间分布上表现出鄱阳湖的上游污染物浓度远小于下游污染值,湖区向出湖口浓度有增高趋势.N/P值从10月份的7.8上升至1月份的31.2,随后下降到4月份的7.4,在7月份又上升至8.9.氮磷营养盐和pH表现出不同的相关关系,如在4月份无机氮和pH的相关系数达0.5.综合各项因子的分析可以得出,潜在性富营养化评价结果是鄱阳湖在调查期间为磷污染比较严重.     

Coral death from sewage and phosphate pollution at Aqaba,Red Sea

Localized pollution of coral reef areas is occurring at Aqaba, Red Sea, as a result of sewage discharge, and as a result of spillage of phosphate dust during loading of phosphate mineral onto ships. The rate of death of colonies of the coral Stylophora pistillata was found to be 4–5 times as great in the polluted area as in a control area. Coral damage in the control area is generally caused by grazing or by extreme low tide, but the cause of coral death in the polluted area was not readily apparent. The growth of algae, both on the damaged corals, and on glass slides placed out in the reef, was greatly stimulated in the polluted area, but it appeared that such algal growth was not the direct cause of coral death. Corals in the polluted area may be under stress because of reduced light intensity, inhibition of calcification by excess phosphate, and increased sediment load. It was found that in the polluted area there was a greater weight of sediment settling on the glass slides for a given weight of algae. But in addition, since algal growth was faster in the polluted area, the sediment load was increased by the sediment trapping capacity of the enhanced algal growth. Thus it is suggested that increased algal growth stimulated by increased nutrient concentrations may be important in greatly increasing the sediment load experienced by corals.     

淡水磷酸盐氧同位素前处理方法的优化

磷是地表水体中的关键性营养盐,在水生生态系统的物质循环与能量流动方面发挥着重要作用,研究水体中磷的来源、转化与归趋对于了解水环境的演变过程与科学保护具有重要意义.近年来,磷酸盐氧同位素(δ18 O P)技术已逐渐应用于淡水环境中磷的来源示踪与生物地球化学循环研究,其样品前处理主要沿用海水方法体系.相比而言,淡水样品中PO 3-4浓度通常较低,有机质和干扰离子含量却较高,复杂的样品前处理过程极大地制约了δ18 O P分析在淡水环境体系的广泛应用.为此,本研究针对现有海水样品δ18 O P前处理方法在地表淡水环境的适用性加以检验,并进行了三点优化改进:①将MAGIC沉淀步骤使用的MgCl 2替换为Mg(NO 3)2,避免了Cl-的干扰,减少AgCl杂质的生成;②调节生成Ag3PO4溶液pH值为8.0,保证Ag3PO4沉淀快速完全;③对Ag3PO4沉淀过程采用避光处理,降低了AgNO 3及Ag3PO4可能的光解影响,提高了Ag3PO4的纯度,使δ18 O P的测试结果更为准确.本改进方法为后续利用δ18 O P技术深入探究淡水环境中磷的生物地球化学循环与生态环境效应提供了有益的方法借鉴.     

What controls levels of dissolved phosphate and ammonium in surface waters?

Dissolved inorganic nutrient pools are small relative to particulate pools, and dissolved pools turnover rapidly. It has been observed that pools change little from day to day on the sampling scales usually employed. A simple model is presented where uptake and regeneration rates balance to cause a local steady state concentration for dissolved inorganic nutrients. Enrichment and dilution perturbation experiments with lake water support the idea of steady state nutrient concentrations. Although inorganic nutrient concentrations are often controlled by biota, the absolute concentrations present tell little about the activity of that biota.     

Patterns of inorganic phosphate uptake in Cassiopea xamachana: a bioindicator species

Nutrient levels in the nearshore waters of the Florida Keys have increased over the past few decades concomitant with a decline in the health of Florida's reef system. Phosphorus is a particular concern in the Florida Keys as it may be the limiting nutrient in nearshore waters. We demonstrate that the upside-down jellyfish, Cassiopea xamachana, decreases its rate of phosphate uptake following exposure to elevated levels of dissolved inorganic phosphate. We also show that this subsequent suppression of uptake rates persists for some time following exposure to elevated phosphates. Using these attributes, we experimentally investigated the use of C. xamachana as a bioindicator for dissolved inorganic phosphates in seawater. Our results show that these animals reveal comparative differences in environmental phosphates despite traditional testing methods yielding no detectable phosphates. We propose that C. xamachana is a bioindicator useful for integrating relevant information about phosphate availability in low nutrient environments.     

Extent of immobilisation of phosphate during aeration of nutrient-rich, anoxic groundwater

Nutrient-rich exfiltrating groundwater may impose a heavy phosphate load on surface water systems. However, iron oxides that bind PO₄ precipitate fast upon oxygenation at neutral pH and PO₄ may also become bound in Ca precipitates following upon pH increase, so load estimates based on conservative behaviour during exfiltration will be overestimates. Aeration experiments using natural groundwater were performed to characterise the immobilisation of PO₄ within one day after aeration started. Groundwaters having a wide variety in composition, were sampled in the coastal lowlands of the Western Netherlands. Three models were considered to describe the fast binding of PO₄ by Fe oxide type phases that form upon the oxygenation of dissolved Fe(II), each based on a different concept. The concepts were surface complexation, solid-solution precipitation and two-mineral precipitation. When the experimental data were compared with model results, all three models were found to be inadequate. Frequently, more immobilisation of PO₄ occurred than could be explained by binding to a Fe oxide type of phase alone. Uptake by Ca phosphates and/or Ca carbonates must additionally have played a role; alternatively, a non-ideal phase consisting of Ca, Fe and PO₄ precipitated upon oxygenation and CO₂ degassing. A predictive multiple regression model with two primary variables that reflect the driving forces for PO₄ immobilisation was deduced that describes immobilisation of phosphate after aeration of anoxic groundwater. The two primary variables are the log value of the groundwater Fe to PO₄ molar ratio and the saturation state for hydroxyapatite after the CO₂ degassing of groundwater. The model is useful for calculating the PO₄ load of surface water from exfiltration groundwater, taking into account fast immobilisation (<1 day) during exfiltration.     

Oxygen isotope variations in phosphate of biogenic apatites,III. Conodonts

The method for measurement of the isotopic composition of oxygen in phosphates has been improved and adapted for analysis of small quantities of apatite, down to 10 mg. This extension enables one to analyze hand-picked conodont samples with an analytical reproducibility better than ±0.5‰ (1σ).46 samples of conodonts ranging from the Ordovician to the Pennsylvanian of North America were analysed. Some insoluble phosphatic residues, ichthyoliths and inarticulate brachiopods of the same time range were also measured. The range of the δ¹⁸O values of the analysed conodonts is between 15 and 19‰. It shows a general trend of decreasing d¹⁸O with increasing age, from an average value of about 19 in the Pennsylvanian to 17 in the Ordovician. This trend parallels that previously detected in marine phosphorites. For the time range between the Devonian and Pennsylvanian our data are in agreement with independent paleoclimatic information. Specifically, we detect maximum¹⁸O enrichment at the end of the Pennsylvanian, and minimum enrichment at the end of the Devonian. The difference between these two extremes is equivalent to about 10°C (from about 40° to 30°C), assuming constant isotopic composition of ocean water.The success of oxygen isotopic analysis of conodonts raises the possibility of their use in Paleozoic paleo-oceanography in a similar way to foraminifera in the Mesozoic-Cenozoic.     

湖泊沉积物中磷酸盐氧同位素前处理方法对比

磷酸盐氧同位素(δ~(18)OP)是一种有效的磷源示踪方式.由于湖泊沉积物的组成十分复杂,必须对样品进行除碳处理和纯化处理.本文对目前应用较为广泛的几种前处理方法进行比较,包括NaClO处理和H_2O_2处理等除有机碳方法,以及Blake法和Mc Laughlin法等纯化方法,以期获得适用于湖泊沉积物磷酸盐氧同位素的前处理方法.结果表明:(1)NaClO处理可以保证较高的无机磷提取效率,同时能有效地减少无机磷提取液中有机质含量,且对不同形态磷的破坏较小;H2O2对有机质的去除效果不稳定,且处理后样品磷形态之间发生转化,显著增加了提取的无机磷浓度.(2)Blake法和Mc Laughlin法分别采用磷钼酸铵(APM)+磷酸铵镁(MAP)沉淀和Ce PO4沉淀对样品进行纯化.在纯化处理湖泊沉积物过程中,Blake法优于Mc Laughlin法,主要体现为有机质去除率高,并且磷的回收率较为稳定.(3)经Blake法纯化丹麦Nordborg湖沉积物样品得到的Ag_3PO_4中C、N含量低于Mc Laughlin法且重现性好.本文结合NaClO法与Blake法的优点,建立了一种适合湖泊沉积物的磷酸盐氧同位素前处理方法:首先用2.5%NaClO对沉积物样品进行除碳预处理,然后对磷酸盐提取液依次通过氢氧化镁共沉淀(MAGIC)、APM+MAP沉淀、阳离子交换树脂处理,最后生成Ag3PO4沉淀.     

Oxygen isotope variations in phosphate of biogenic apatites,II. Phosphorite rocks

Phosphorites from sedimentary sequences ranging in age from Archaean to Recent were analysed for δ¹⁸O in both the PO₄ (δ¹⁸O_p) and CO₃ (δ¹⁸O_c) in the apatite lattice. The oxygen isotope record is considerably better preserved in phosphates than in either carbonates or cherts. The use of the Longinelli and Nuti [8] temperature equation yields temperatures for Recent phosphorites that are in good agreement with those measured in the field. The δ¹⁸O_p values of ancient phosphorites decrease with increasing age. These changes with time are not likely to be due to post-depositional exchange. Changes in δ¹⁸O values of seawater and variations of temperature with time can account for the δ¹⁸O_p time trend, but the latter explanation is preferred. In Ancient phosphorites δ¹⁸O_c in structurally bound carbonate in apatite is not a reliable geochemical indicator.     

Lime incrustingHapalosiphon intricatus (Cyanophyceae) and phosphate availability in a Florida cave

Hapalosiphon intricatus (Cyanophyceae) with lightly calcified sheaths, is the dominant filamentous alga reported from a humid, dimly-lighted limestone cave in northcentral Florida (USA). Within the limestone substrate, hydroxyapatite is the form of the phosphate mineral providing nutrient to the algae. Florida Agricultural Experiment Station Journal series No. 4381.