Sources and bioavailability of phosphorus fractions in freshwaters: a British perspective

This paper seeks a perspective on the forms of phosphorus which promote aquatic eutrophication, with the particular quest of establishing their sources. A short background traces the development of understanding of nutrient enrichment and the suppositions about the relative contributions of agriculture, sewage and detergent residues. Most aquatic systems, and their primary producers, are naturally deficient in biologically-available phosphorus. Aquatic plants have evolved very efficient phosphorus uptake mechanisms. The biomass responses to an increase in the supply of phosphorus are stoichiometrically predictable. The most bioavailable forms of phosphorus are in solution, as orthophosphate ions, or are readily soluble or elutable from loose combinations. Ready bioavailability coincides well with what is measurable as molybdate-reactive (MRP) or soluble-reactive phosphorus (SRP). Most other forms, including phosphates of the alkaline earth metals, aluminium and iron are scarcely available at all. Orthophosphate ions sorbed to metal oxides and hydroxides are normally not biologically available either, except through weak dissociation ('desorption'). The production of alkaline phosphatase provides organisms with an additional mechanism for accelerating the sequestration of phosphate from organic compounds. Bioavailable phosphate is liberated when redox- or alkali-sensitive metal hydroxides dissolve but these processes are minor contributors to the biological responses to nutrient enrichment. Most of the familiar eutrophication is attributable to the widespread application of secondary sewage treatment methods to the wastes emanating from a burgeoning and increasingly urbanised human population. The use of polyphosphate-based detergents, now in decline, has contributed to the problem. In aquatic systems, the additional phosphorus raises the biological supportive capacity, sometimes to the capacity of the next limiting factor (carbon, light, hydraulic retention or of another nutrient). At high orthophosphate loadings, the straight stoichiometric yield relationship between biomass yield and phosphorus a vailability is lost. Movements of phosphorus and its recycling within aquatic systems do not prevent the slow gravitation of phosphorus to the bottom substrata. The phosphorus retentivity of sediments depends upon their chemical composition. While oxide-hydroxide binding capacity in the surface sediments persists, they act as a sink for phosphorus and a control on further cycling. Iron-rich and clay-rich sediments perform best in these conditions; calcareous sediments least so. Eutrophication may lead to the exhaustion of sediment P-binding capacity. Non-sorbed phosphate is readily recyclable if primary producers have access to it. Recycling is most rapid in shallow waters (where sediment disturbance, by flow, by wind action and through bioturbation, is frequent and least in deep ventilated sediments. The contributions of phosphorus from catchments are assessed. The slow rate of weathering of (mostly apatitic) minerals, the role of chemical binding in soils and the incorporation and retentivity bv forested terrestrial ecosystems each contribute to the minimisation of phosphorus leakage to drainage waters. Palaeolimnological and experimental evidence confirms that clearance of land and ploughing its surface weakens the phosphorus retentivity of catchments. The phosphorus transferred from arable land to drainage remains dominated by sorbed fractions which are scarcely bioavailable. Some forms of intensive market gardening or concentrated stock rearing may mobilise phosphates to drainage but it is deduced that drainage from agricultural land is not commonly a major source of readily bioavailable phosphorus in water. Careful budgeting of the phosphates in run-off from over-fertilised soils may nevertheless show that a proportionately small loss of bioavailable phosphorus can still be highly significant in promoting aquatic plant production. The bioavailable-phosphorus (BAP) load achieving the OECD threshold of lake eutrophy (35 mg P m(-3)) is calculated to be equivalent to a terrestrial loss rate of approximately 17.5 kg BAP km(-2) year(-1)), or only 1-2% of a typical fertiliser application. The output is shown to be comparable with the P yield from secondary treatment of the sewage produced by a resident population of 30-44 persons km(-2). With tertiary treatment, the equivalence is with approximately 200 persons km(-2).     

Inositol phosphates in the environment

The inositol phosphates are a group of organic phosphorus compounds found widely in the natural environment, but that represent the greatest gap in our understanding of the global phosphorus cycle. They exist as inositols in various states of phosphorylation (bound to between one and six phosphate groups) and isomeric forms (e.g. myo, D-chiro, scyllo, neo), although myo-inositol hexakisphosphate is by far the most prevalent form in nature. In terrestrial environments, inositol phosphates are principally derived from plants and accumulate in soils to become the dominant class of organic phosphorus compounds. Inositol phosphates are also present in large amounts in aquatic environments, where they may contribute to eutrophication. Despite the prevalence of inositol phosphates in the environment, their cycling, mobility and bioavailability are poorly understood. This is largely related to analytical difficulties associated with the extraction, separation and detection of inositol phosphates in environmental samples. This review summarizes the current knowledge of inositol phosphates in the environment and the analytical techniques currently available for their detection in environmental samples. Recent advances in technology, such as the development of suitable chromatographic and capillary electrophoresis separation techniques, should help to elucidate some of the more pertinent questions regarding inositol phosphates in the natural environment.     

A comparison of phosphorus immobilization in sediments of freshwater and coastal marine systems

The extent to which sediments of aquatic systems immobilize or release phosphorus can affect dramatically the P content of overlying waters. Data from 48 different aquatic systems suggests that there may be a major difference between fresh- and salt-water systems in this immobilization. Under oxic conditions (water overlying sediments had dissolved oxygen > 0.5 mg/L) P is strongly immobilized in sediments of most fresh-water systems. In sediments of most salt-water systems P is released from sediments and behaves, essentially, as a conservative tracer of benthic decomposition. This difference in P cycling is large enough to have an influence on the often cited difference in phytoplankton nutrient limitation between fresh- and salt-water systems.     

白浆土 植物系统营养物质转化机制及其有效性研究Ⅳ.环境条件对土壤磷素有效性的影响

根际试验研究表明,水分、有机质、土壤酸度是影响白浆土磷素生物有效性的重要因子。调节土壤水分含量,能增强土壤中铁、铝磷酸盐的溶解,加速磷酸根离子从根际土壤向非根际土壤扩散。增加土壤有机质含量,降低了土壤对P素的吸附自由能(K值),提高土壤中的速效磷含量。适量施用石灰,调节白浆土酸度,由于化学溶解作用的影响,促进了土壤中铁、铝磷酸盐的溶解,增强了土壤中磷素的生物有效性.     

白浆土植物系统营养物质转化机制及其有效性研究Ⅳ.环境条件对土壤磷素有效性的影响

根际试验研究表明,水分、有机质、土壤酸度是影响白浆土磷素生物有效性的重要因子．调节土壤水分含量,能增强土壤中铁、铝磷酸盐的溶解,加速磷酸根离子从根际土壤向非根际土壤扩散．增加土壤有机质含量,降低了土壤对Ｐ 素的吸附自由能（ Ｋ 值） ,提高土壤中的速效磷含量．适量施用石灰,调节白浆土酸度,由于化学溶解作用的影响,促进了土壤中铁、铝磷酸盐的溶解,增强了土壤中磷素的生物有效性     

Available phosphorus in lake sediments in The Netherlands

The amount of phosphorus available to algae in the sediments of four lakes in the western part of the Netherlands has been assessed by means of chemical extraction and bioassay techniques. In addition to direct chemical sediment analyses, extractions were carried out with an NTA column method and a stepwise NH₄ Cl-NaOH-HCI shaking method, the latter supposedly separating the weakly bound, the Fe- and Al-bound and the Ca-bound phosphates in the sediments. Bioassays, with sediment as the sole source of P, were made withScenedesmus quadricauda in modified Skulberg's 28 medium to determine the amount of phosphates available to algae.The average total P concentration of the sediments varied from 0.8 to 3.6 mg P g^–1 dry wt and correlated well with the net external P loading of the lakes. Uptake of P by algae in the bioassays varied from 0.4 to 36% — while NTA extracted 36–69% of the total P. The ratio NH₄Cl extracted/ NaOH extracted/ HCI extracted phosphates is different from lake to lake, although in all lakes the highest extractions (27–62% of total P) are found in the NaOH fraction. However, in the peaty sediments of these lakes, the NaOH step extracted not only the Fe- and Al-bound phosphates but, also, large amounts of humus compounds. Hence, this fraction also contains non-available organic P.The results are related to soil type and chemical characteristics of the sediments, and compared with data from other authors. A positive correlation was found between phosphate available to algae and NTA- and NaOH-extractable P, but the correlation with total phosphorus was higher. Moreover, algal-extractable P proved to be positively correlated with total iron and clay content and negatively with the amount of organic matter.It is concluded that the sediments in the investigated lakes show great variability and that the chemical extraction techniques cannot replace the bioassays to assess the amount of phosphorus available to algae.     

Influence of aquatic macrophytes on phosphorus cycling in lakes

Emergent macrophytes take up their phosphorus exclusively from the sediment. Submerged species obtain phosphorus both from the surrounding water and from the substrate, but under normal pore and lake water phosphorus concentrations, substrate uptake dominates. Release of phosphorus from actively growing macrophytes (both submerged and emergent) is minimal and epiphytes obtain phosphorus mainly from the water. Decaying macrophytes may act as an internal phosphorus source for the lake and add considerable quantities of phosphorus to the water. A large part of the released phosphorus is often retained by the sediments. In perennial macrophytes the amount of phosphorus released from decaying shoots is dependent on the degree of phosphorus conservation within the plant. Macrophyte stands may also be a permanent phosphorus sink due to burial of plant litter. Macrophytes affect the chemical environment (oxygen, pH), which in turn has effects on the phosphorus cycling in lakes. However, the impact of aquatic macrophytes on whole-lake phosphorus cycling is largely unknown. Controlled full-scale harvesting, herbicide or herbivory experiments are almost totally lacking. Emergent macrophytes respond positively to eutrophication, but fertilization experiments have shown that nitrogen rather than phosphorus may be the key element. Submerged macrophytes are adversely affected by a large increase in the external phosphorus input to a lake. This effect may be caused by epiphyte shading, phytoplankton shading or deposition of unfavourable sediments.     

The Ratios of Carbon,Nitrogen, and Phosphorus in a Wetland Coastal Ecosystem of Southern India

The fertility of the coastal and estuarine waters is of great concern because of its influence on the productivity of these waters. Seasonal variations in the distribution of organic carbon, total nitrogen and total phosphorus in the sediments of Kuttanad Waters, a part of the tropical Cochin Estuary on the south west coast of India, are examined to identify the contribution of sediments to the fertility of the aquatic systems. The adjoining region has considerable agricultural activity. The fresh water zones had higher quantities of silt and clay whereas the estuarine zone was more sandy. Organic carbon, total phosphorus and total nitrogen were higher in the fresh water zones and lower in the estuarine zones. Total phosphorus and organic carbon showed the lowest values during monsoon periods. No significant trends were observed in the seasonal distributions of total nitrogen. Ratios of C/N, C/P and N/P, and the phosphorus and nitrogen content indicate significant modification in the character of the organic matter. Substantial amounts of the organic matter can contribute to reducing conditions and modify diagenetic processes.     

Release rates and biological availability of phosphorus released from sediments receiving aquaculture wastes

Aquaculture is an increasingly significant user of freshwater resources in Scotland. In 1989, the total fish biomass produced in Scottish freshwater amounted to 7000 t. 50% of this total was reared in floating cage systems situated in lochs (lakes). Both solid (mainly in the form of uneaten feeds and faecal matter) and dissolved byproducts of the production cycle enter the limnetic environment untreated. Much solid waste material accumulates directly on the sediments beneath the cage systems. This leads to a localised enrichment in nutrient elements of the sedimentary environment. The experiments served to quantify rates of total phosphorus (TP) and dissolved reactive phosphorus (DRP) release from undercage and control sites, and to relate such releases to the biological availability of the released P. Results indicate significantly higher levels of NH₄Cl-extractable P in sediments affected by waste deposition from fish cages. TP and DRP release, and greater growth of Chla are obtained from undercage cores compared with control sites. No link between extractable-P content of sediments, or release rate and Chla production was established.     

Beta-propeller phytases in the aquatic environment

Phytate, which is one of the dominant organic phosphorus compounds in nature, is very stable in soils. Although a substantial amount of phytate is carried from terrestrial to aquatic systems, it is a minor component of organic phosphorus in coastal sediments. The ephemeral nature of phytate implies the rapid hydrolysis of phytate under aquatic conditions. Among the four classes of known phytases that have been identified in terrestrial organisms, only β-propeller phytase-like sequences have been identified in the aquatic environment. A novel β-propeller phytase gene (phyS), cloned from Shewanella oneidensis MR-1, was found to encode a protein with two beta-propeller phytase domains. The characterization of recombinant full-length PhyS and its domains demonstrated that Domain II was the catalytic domain responsible for phytate hydrolysis. The full-length PhyS displayed a K_m of 83 μM with a kcat of 175.9 min⁻¹ and the Domain II displayed a K_m of 474 μM with a kcat of 10.6 min⁻¹. These results confirm that the phyS gene encodes a functional β-propeller phytase, which is expressed in S. oneidensis under phosphorus deficienct condition. The presence of multiple sequences with a high similarity to phyS in aquatic environmental samples and the widespread occurrence of the Shewanella species in nature suggest that the β-propeller phytase family is the major class of phytases in the aquatic environment, and that it may play an important role in the recycling of phosphorus.     

Presence of and phosphate release from polyphosphates or phytate phosphate in lake sediments

NaOH is often used as an extractant for thefractionation of sediment-bound phosphates. Besidesorthophosphate, a certain quantity of phosphate whichis called ‘non-reactive NaOH-extractable phosphate’is also extracted. In recent literature it has beensuggested that this fraction consists of bacterialpolyphosphates and might be responsible for the phosphate release from aquatic sediments under anoxicconditions. In a previous publication we have already shown thatNaOH is not an accurate extractant as both theconcentration of NaOH and the duration of theextraction have an influence on the quantity ofphosphate extracted, due to the hydrolysis of organicphosphates. In this article we show that cold NaOH does not onlyextract iron-bound phosphate but phytate phosphate aswell. Non-reactive phosphate in this extract was notrelated to the presence of polyphosphate, but mainlyto phytate and humic phosphates. As it has been shownthat phytate may disappear from sediments when theybecome anoxic, we suggest that phytate mineralizationmay be an important mechanism for anoxic phosphaterelease from sediments. This revised version was published online in July 2006 with corrections to the Cover Date.     

土壤微孔对有机物吸附/解吸的影响及其表征

土壤吸附是影响环境中有机化合物迁移、降解及生物有效性的重要过程,而微孔的存在是影响有机化合物慢吸附过程的重要因素之一,土壤孔隙结构(pore structure)及土壤微孔的研究对于理解发生在土壤中的吸附/解吸过程十分必要.综述了近年来土壤微孔对有机化合物吸附解吸行为影响的研究态势,包括土壤的孔隙结构及微孔的存在形式、微孔吸附有机化合物的吸附动力学和可能机理、土壤中微孔表征的技术方法、孔隙大小分布的计算以及对未来的研究展望,以期对土壤有机污染生物修复的深入研究提供理论依据.     

Acquisition of phosphorus and nitrogen in the rhizosphere and plant growth promotion by microorganisms

The rhizosphere is a complex environment where roots interact with physical, chemical and biological properties of soil. Structural and functional characteristics of roots contribute to rhizosphere processes and both have significant influence on the capacity of roots to acquire nutrients. Roots also interact extensively with soil microorganisms which further impact on plant nutrition either directly, by influencing nutrient availability and uptake, or indirectly through plant (root) growth promotion. In this paper, features of the rhizosphere that are important for nutrient acquisition from soil are reviewed, with specific emphasis on the characteristics of roots that influence the availability and uptake of phosphorus and nitrogen. The interaction of roots with soil microorganisms, in particular with mycorrhizal fungi and non-symbiotic plant growth promoting rhizobacteria, is also considered in relation to nutrient availability and through the mechanisms that are associated with plant growth promotion.     

New pathways for ammonia conversion in soil and aquatic systems

Ammonia conversion processes are essential for most soil and aquatic systems. Under natural conditions, the many possible reactions are difficult to analyze. For example, nitrification and denitrification have long been regarded as separate phenomena performed by different groups of bacteria in segregated areas of soils, sediments or aquatic systems sequentially in time. It has now been established that strict segregation in place and time of the two processes is not necessary and that both denitrifiers and nitrifiers have versatile metabolisms. However, the rates described for aerobic denitrifiers are very low compared to the rates observed under anoxic conditions. Also the rates of nitrifier denitrification are quite low, indicating that these conversions may not play an important role under natural conditions. In addition, these processes often result in the emission of quite large amounts of undesirable products, NO and N₂O. Heterotrophic nitrification might be of relevance for systems, that contain a high carbon to nitrogen ratio. Recently, a novel process (Anammox) has been discovered in which ammonium serves as the electron donor for denitrification of nitrite into dinitrogen gas. ¹⁵N labeling studies showed that hydrazine and hydroxylamine were important intermediates in this process. Enrichment cultures on ammonium, nitrite and bicarbonate resulted in the dominance of one morphotypical microorganism. The growth rate of the cultures is extremely low (doubling time 11 days), but the affinity for ammonium and nitrite and the conversion rates (9.2 10^–4 mol kg^–1 s^–1) are quite high. Some of the reported high nitrogen losses in soil and aquatic systems might be attributed to anaerobic ammonium oxidation. In addition, this conversion offers new opportunities for nitrogen removal, when it is combined with recently developed processes for partial nitrification.     

Restoring natural seepage conditions on former agricultural grasslands does not lead to reduction of organic matter decomposition and soil nutrient dynamics

In the central part of the Netherlands, wetland restoration projects involve the rewetting of former agricultural land, where low water levels were artificially maintained (polders). Many of these projects do not result in the expected reduction of nitrogen and phosphorus availability and subsequent re-establishment of a diverse wetland vegetation. The aim of the present study was to investigate which mechanisms are responsible for this lack of success. Thereto, we studied the effect of rewetting of former agricultural grasslands on acidified peat soil (pH = 3.5) on organic matter decomposition, nitrogen cycling and phosphorus availability in the soil for three seasons. To provide an explanation for the observed effects, we simultaneously studied a set of potentially controlling abiotic soil conditions that were expected to change after rewetting. It was found that rewetting of these grasslands with natural, unpolluted seepage water did not affect nitrogen cycling, but raised decomposition rates and almost doubled phosphorus availability. The main cause of these effects is a raise of soil pH to about 7 due to the hydrochemical composition of the soil pore water after rewetting, which reflects groundwater with high amounts of buffering ions. This effect overruled any reduction in process rates by the lowered soil redox potential. The counterintuitive finding of eutrophication after rewetting with natural and unpolluted water is considered to represent a new form of internal eutrophication, triggered by the restoration of natural site conditions of former agricultural land on acid peat soil.     

Distribution of Clostridium botulinum.

The distribution of Clostridium botulinum in the natural environments of Denmark, The Faroe Islands, Iceland, Greenland, and Bangladesh was examined. A total of 684 samples were tested. Type E was found in 90% of samples from the aquatic environment of Denmark, including sediments from young artificial lakes, and in 86% of samples from the marine environment of Greenland. Type E was not found in Danish cultivated soil and woodlands, including cultivated soil from reclaimed sea beds, but type B was frequently demonstrated in these environments. C. botulinum types A, B, or E were found in 2.6% of samples from the environments of the Faroe Islands and Iceland, whereas types C or D were demonstrated in 42% of samples from Bangladesh. The incidence of type E in aquatic sediments was not related to general industrial pollution or a high content of rotting vegetation. Fish or a rich aquatic fauna, on the other hand, appeared to contribute to a high incidence of type E. Based on these findings, it is suggested that type E is a true aquatic organism, because this environment offers the best conditions for survival of the spore in nature. It is further suggested that its presence in aquatic bottom deposits is based on sedimentation after proliferation in the carrion of the aquatic fauna and dissemination by water currents and migrating fish.     

Soil Organic Phosphorus Transformations During Pedogenesis

Abstract Long-term changes in soil phosphorus influence ecosystem development and lead to a decline in the productivity of forests in undisturbed landscapes. Much of the soil phosphorus occurs in a series of organic compounds that differ in their availability to organisms, but changes in the relative abundance of these compounds during pedogenesis remain unknown. We used alkaline extraction and solution phosphorus-31 nuclear magnetic resonance spectroscopy to assess the chemical nature of soil organic phosphorus along a 120,000-year post-glacial chronosequence at Franz Josef, New Zealand. Inositol phosphates, DNA, phospholipids, and phosphonates accumulated rapidly during the first 500 years of soil development characterized by nitrogen limitation of biological productivity, but then declined slowly to low concentrations in older soils characterized by intense phosphorus limitation. However, the relative contribution of the various compounds to the total organic phosphorus varied along the sequence in dramatic and surprising ways. The proportion of inositol hexakisphosphate, conventionally considered to be relatively recalcitrant in the environment, declined markedly in older soils, apparently due to a corresponding decline in amorphous metal oxides, which weather to crystalline forms during pedogenesis. In contrast, the proportion of DNA, considered relatively bioavailable in soil, increased continually throughout the sequence, due apparently to incorporation within organic structures that provide protection from biological attack. The changes in soil organic phosphorus coincided with marked shifts in plant and microbial communities, suggesting that differences in the forms and bioavailability of soil organic phosphorus have ecological significance. Overall, the results strengthen our understanding of phosphorus transformations during pedogenesis and provide important insight into factors regulating the composition of soil organic phosphorus.     

Development and practical application of limiting values for the phosphate concentration in surface waters in the Netherlands

Summary To counteract eutrophication it is important to possess sufficient information (1) on the relationship between the content of nutrients and the algal biomass, and (2) on the cycling of nutrients in lakes.A comparative study of a large number of surface waters in the Netherlands has demonstrated that it is possible to derive a relationship between the nitrogen and phosphorus concentrations and the upper limit of the chlorophyll concentration, averaged over the summer season.For the authority in charge of water quality it is essential to know how far the phosphorus loading must be reduced to attain the desired phosphate concentration. The results of an extensive study of the nutrient budgets of Lake Wolderwijd-Nuldernauw over the period 1976–1979 demonstrate that in certain cases a relative high phosphate concentration can occur (approx. 0.30 mg/l) in spite of a low external phosphorus loading (approx. 0.7 g P/m² year). Such high concentrations can be explained by the continuous presence of a bloom of blue-green algae and the release of phosphate from the aquatic sediments during the summer. In such lakes it is necessary to take additional measures, such as flushing with water poor in algae and phosphates, or, where necessary, the removal of aquatic sediment rich in phosphate.     

有机污染物的土壤微界面过程及其影响因素

土壤是环境的重要组成部分,是连接大气圈、水圈、岩石圈和生物圈的纽带。随着工农业生产的迅速发展,越来越多的有机污染物通过各种途径进入土壤环境。本文主要对有机污染物在土壤中的吸附-解吸、降解-积累、溶解-沉淀等微界面过程进行了较为系统的阐述,探讨了土壤有机组分、无机组分、植物和微生物等生态因子对有机污染物相关土壤微界面过程的影响;同时,结合国内外的研究现状和趋势,对今后土壤微界面过程的研究方向以及采用的方法手段进行了建议和展望。     

Effects of nitrogen: phosphorus supply ratios on nitrogen fixation in agricultural and pastoral ecosystems

An analysis of data compiled from the literature confirms a strong inverse relationship between annual rates of nitrogen fixation and the soil nitrogen content in agricultural and pastoral ecosystems. However, this inverse relationship is strongly modified by the rate of application of phosphorus fertilizer, which strongly influences the activities of both symbiotic and non-symbiotic nitrogen fixing organisms. In the case of symbiotic legumes, the response of N-fixation to N and P is in part a result of changes in legume dominance within the plant community. These results, as well as supporting data presented from a review of experiments on nitrogen fixation in a variety of other terrestrial and aquatic ecosystems, provide important support for the hypothesis that phosphorus availability is a key regulator of nitrogen biogeochemistry. Published as Paper No. 9950, Journal Series, Nebraska Agricultural Research Division, University of Nebraska, Lincoln, NE, USA.