Environmental dynamics of phosphate esters. II. Uptake and bioaccumulation of 2-ethylhexyl diphenyl phosphate and diphenyl phosphate by fish

Uptake, clearance and disposition of ¹⁴C-labelled 2-ethylhexyl diphenyl phosphate (EHDP) and ¹⁴C-diphenyl phosphate (DPP) by rainbow trout (Salmo gairdneri) were investigated using short-term static exposures. Bioconcentration factors of 1314 and 0.3 were calculated for EHDP and DPP, respectively. Highest levels of radioactivity were found in liver and intestine following exposure to 60 μg/L EHDP. A portion (up to 40%) of the radioactivity in each tissue was in the form of DPP while a similar portion was extractable with methanol but could not be identified.     

青萍(Lemna minor L.)对氮磷的吸收特征

以西部地区优势浮萍品种青萍为实验对象,研究了青萍对不同浓度硝态氮和磷酸盐的吸收特征。结果表明,硝态氮浓度在1～10 mg/L范围内,青萍对硝态氮有较好的吸收效果,M-M方程可以较好地描述硝态氮浓度与青萍对硝态氮的吸收速率之间的关系,通过M-M方程拟合得到青萍对硝态氮的最大吸收速率为0.1167 mg/(g FW.h),亲和力常数为6.9274。磷酸盐浓度在0.1～1.0 mg/L范围内,青萍对磷酸盐也有较好的吸收效果,二次多项式回归可以较好地描述青萍吸收速率与磷酸盐浓度的关系,回归方程得到青萍对磷酸盐的最大吸收速率为0.0193 mg/(g FW.h),对应磷酸盐浓度为0.6 mg/L。     

Biological phosphate uptake and release: effect of pH and magnesium ions.

Enhanced biological phosphorus removal (EBPR) is based on poly-phosphate accumulating organisms' (PAOs) unique features of "luxury" phosphate uptake during aerobic conditions and phosphate release in anaerobic conditions. It is believed that poly-phosphate accumulation is accompanied by the uptake and accumulation of potassium ions (K+) and magnesium ions (Mg2+). The release of phosphate under anaerobic conditions is also accompanied by the release of both cations. The objective of this research was to evaluate the effect of pH and Mg2+ on the biological phosphate uptake and release behavior of activated sludge mixed liquor during aeration and sedimentation. Research results indicate that Mg2+, supplied either by magnesium chloride (MgCl2) or magnesium hydroxide [Mg(OH)2], stimulated phosphate uptake during the aeration period, while pH increase, caused by the application of Mg(OH)2, enhanced phosphate release during the sedimentation period. It is also noted in our experiments with MgCl2 that Mg2+ slightly inhibited anaerobic phosphate release.     

Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

亚硝酸对聚磷菌好氧吸磷抑制作用研究

为确定亚硝酸对聚磷菌好氧吸磷的抑制作用,利用批量实验研究了在不同pH下不同浓度的亚硝态氮对聚磷菌好氧吸磷过程的影响.实验结果表明,亚硝酸对聚磷菌好氧吸磷具有更直接的影响;亚硝酸质量浓度达到0.001 00 mg/L时,聚磷菌好氧吸磷即会受到50％的抑制.聚磷菌受到较低浓度的亚硝酸抑制时,其在无亚硝酸存在的环境中好氧吸磷能力基本能恢复.     

Effect of phosphate fertilizer application on phosphorus (P) losses from paddy soils in Taihu Lake Region. I. Effect of phosphate fertilizer rate on P losses from paddy soil

A field plot study was conducted on two types of paddy soils in the Taihu Lake Region, during the rice season of year 2000 in order to assess phosphorus (P) losses by runoff and vertical leaching, which are considered the two main pathways of P movement from paddy soil into its surrounding water course. Commercial NPK compound fertilizer and single superphosphate fertilizer were applied to furnish 0, 30, 150, and 300 kg applied P ha m(-2). The experiments consisted of three replicates of each treatment in Changshu site and four replicates in Anzhen site, with a plot size of 5 x 6 m2 in a randomized block. Results revealed that the average concentration range for total P (TP) in runoff was 1.857-7.883, 1.038-5.209, 0.783-1.255 and 0.572-0.691 mg P l(-1) respectively for P300, P150, P30 and P0 in Anzhen, while it was 2.431-2.449, 1.578-1.890, 1.050-1.315 and 0.749-0.941 mg P l(-1) respectively in Changshu. In all treatments, particulate P (PP) represented a major portion of the TP lost in runoff, it was 80% in Anzhen, and it was even more (>90%) in Changshu. Phosphate fertilizer treatments significantly affected P concentrations and P loads in the runoff. The mean concentration and average seasonal TP load from the P150 plots were 1.809 mg P l(-1) and 395 g P ha m(-2) season(-1) respectively, and lower than that from the P300 plots (2.957 mg P l(-1) and 652 g P ha m(-2) season(-1)). These were obviously higher than from the P30 (0.761 mg P l(-1) and 221 g P ha m(-2) season(-1)) and P0 (0.484 mg P l(-1) and 146 g P ha m(-2) season(-1)) respectively. There was no significant difference found between the P30 and the P0 in both sites. Under usual P application rate, there were total 31.7 and 20.6 tones P removed by runoff from permeable (Anzhen site) and waterlogged (Changshu site) paddy soils in the southern Jiangsu region (major part of the TLR) in the rice season of the year 2000. But if the P application rate is unusual high, or the Olsen P in soil accumulates to above a certain level, then this could sharply increase in the future. The average concentration of molybdate reactive phosphorus (MRP) in the vertical leachate from the four different P treatments ranged from 0.058 to 0.304 mg P l(-1) in Anzhen and from 0.048 to 0.394 mg P l(-1) in Changshu. P application rate significantly affected the MRP concentration at each depth in both sites, except for the 90 cm in Anzhen. The average MRP loads during the rice season moved by vertical leaching from the four treatments ranged from 163 to 855 g P ha m(-2) season(-1) in Anzhen and 208-1,825 g P ha m(-2) season(-1) in Changshu. Vertical leachate movement does not necessarily mean that it moves towards surface water and contaminate the watercourses in this flat plain paddy soil region, it does, however, imply that P can move down from surface layers of soil to deeper levels.     

Effects of solution conditions on the precipitation of phosphate for recovery. A thermodynamic evaluation

To understand the effects of solution conditions on the precipitation of calcium phosphates from wastewater for recovery, a computer programme PHREEQC was employed to calculate the speciation and saturation-index (SI) with respect to hydroxyapatite of a chemically defined precipitation system, which contains phosphate of 1–200 mg P/l, with Ca/P molar ratios of one to 10 times of the stoichiometric calcium to phosphorus molar ratio of hydroxyapatite, at a pH range of 7.0–11.0. The results show that the SI is respectively the logarithmic function of the phosphate concentration and the calcium concentration, increasing with the increase of either of them; the SI is a polynomial function of the solution pH value and increases with its increase, and the effect of solution pH value is due to its influence on base uptake of the precipitation reaction and the speciation of phosphate and calcium ions; the SI is also a logarithmic function of the solution ionic strength but decreases with its increase; at the temperature range of 5–30 °C the SI increases linearly with solution temperature and the effect of temperature is also due to its influence on the speciation of phosphate and calcium ions.     

页岩陶粒对水体中磷的吸附作用及动力学

研究了页岩陶粒对水溶液中磷的等温吸附特征,考察了溶液磷初始浓度、吸附剂粒径和温度对吸附作用的影响,利用一级和准二级动力学模型对页岩陶粒吸附除磷动力学过程进行了分析.结果表明,页岩陶粒对磷的等温吸附特征符合Langmuir方程,最大磷吸附量为131.58 mg/kg.溶液磷初始浓度越大,温度越高,页岩陶粒对磷的吸附量越大.随着吸附剂粒径的减小,一级动力学速率常数增大,吸附平衡时间缩短.尽管一级和准二级动力学模型都能反映不同条件下页岩陶粒的吸附除磷动力学过程,但相比较而言,准二级动力学对该过程的描述更为准确,由该模型估算出页岩陶粒对磷的平衡吸附量qe,其误差基本小于13.00%.     

Timing of phosphate application affects arsenic phytoextraction by Pteris vittata L. of different ages

The effects of timing in phosphate application on plant growth and arsenic removal by arsenic hyperaccumulator Pteris vittata L. of different ages were evaluated. The hydroponic experiment consisted of three plant ages (A45d, A90d and A180d) and three P feeding regimens (P200+0, P134+66 and P66+134) growing for 45 d in 0.2-strength Hoagland-Arnon solution containing 145 microg L(-1) As. While all plants received 200 microM P, P was added in two phases: during acclimation and after arsenic exposure. High initial P-supply (P200+0) favored frond biomass production and plant P uptake, while split-P application (P134+66 and P66+134) favored plant root production. Single P addition favored arsenic accumulation in the roots while split-P addition increased frond arsenic accumulation. Young ferns (A45d) in treatment P134+66 were the most efficient in arsenic removal, reducing arsenic concentration to below 10 microg L(-1) in 35 d. The results indicated that the use of young ferns, coupled with feeding of low initial P or split-P application, increased the efficiency of arsenic removal by P. vittata.     

Lead phosphate formation in soils

Pyromorphite (Pb5(PO4)3Cl) is one of the most thermodynamically stable lead minerals under the geochemical conditions prevailing in the surface environment. It is therefore expected to form in soils contaminated with Pb if sufficient phosphorus is available. Pyromorphite has previously been identified in mine-waste and industrially contaminated soils but has not previously been identified in urban soils. This paper reports on the presence of a Pb phosphate in urban and roadside soils. This phase has formed in the soil as a weathering product of Pb-bearing grains. Quantitative EDX analyses indicated that the Pb phosphate phase is pyromorphite with Ca frequently substituting for Pb between 21-31 atomic percent. However, positive identification of this phase by XRD was hindered by the deviation from pure end-member and possibly also by the poorly crystalline nature of the phase. Pyromorphite accounted for less than 2% of the total Pb in these soils. However, phosphate amendments to the soil could induce further formation of pyromorphite. As pyromorphite is a highly insoluble mineral, this may be effective in reducing the bioavailability of Pb in urban soils.     

Dynamics of isopropylphenyl diphenyl phosphate in fathead minnows

The fate of a triaryl phosphate (ring-UL-¹⁴C-2-isopropylphenyl diphenyl phosphate) was examined in fathead minnows. Diphenyl phosphate was identified as a major metabolite in whole body fish samples. A significant portion of the radioactive residues appeared to be associated with biogenic compounds, indicating “in vivo” reactions of biochemicals with ¹⁴C-metabolites or ¹⁴C-ring cleavage of 2-isopropylphenyl diphenyl phosphate and subsquent incorporation into biochemical pathways.     

Calcite-seeded crystallization of calcium phosphate for phosphorus recovery

For phosphorus recovery from wastewater, the present paper aims at understanding the crystallization of calcium phosphate by using calcites (Juraperle and Coccolith) as seeds from hard water. Synthetic hard water with 60 mgCl(-1) carbonate and 10 mgPl(-1) phosphate was prepared and used in the batch experiments of calcite-seeded crystallization. The solution composition was measured throughout the batch crystallization process, and the corresponding saturation indices with respect to the minerals were calculated with PHREEQC Program. The surface of the calcite seeds was observed and measured with environmental scanning electron microscopy (ESEM), Fourier transform infrared (FTIR) and BET method. The studies show that both calcites are effective seeds for the crystallization of calcium phosphate from hard water; the used calcites are more efficient than the original ones because newly formed crystals with calcium phosphate have covered their surfaces. The studies show that the calcite seeds can be used for phosphorus recovery from hard waters.     

Mg-Al-Cl-LDH对磷的吸附性能及其机理

通过成核/晶化隔离法制备了氯离子型镁铝层状双金属氢氧化物(Mg-Al-Cl-LDH),并用于磷酸盐的吸附;借助扫描电镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FT-IR)、X射线光电子能谱(XPS)进行了表征,并探究其吸附磷酸盐的机理.结果表明:当pH为4～7时,Mg-Al-Cl-LDH对磷的吸附效果较好,而在碱性条件下吸附量会下降;磷质量浓度为50mg·L-1,当pH为5时,Mg-Al-Cl-LDH投加量为2g·L-1时,磷去除率可达到100％;共存离子CO32-会对吸附产生一定影响,当CO32-质量浓度为50mg·L-1时,磷去除率由87％降低到63％.Mg-Al-Cl-LDH对磷的吸附过程在前15 min迅速,90min时达到平衡,符合准二级动力学和Sips吸附等温模型,说明主要吸附过程以化学吸附为主,理论最大吸附量为62.46mg·g-1o表征结果表明,Mg-Al-Cl-LDH为典型的六边形层片结构,吸附后依旧保持该结构.Mg-Al-Cl-LDH对磷的吸附机理主要为静电吸引、层间阴离子交换、配体交换过程.     

Adsorption of phosphate from aqueous solution onto alunite

The phosphate removal potential of alunite, a low cost and abundantly available material, has been investigated. The effects of calcination temperature and time of alunite, adsorbent particle size, pH and initial phosphate concentration on the phosphate adsorption by the calcined alunite have been studied. Phosphate removal was seen to increase with increasing calcination temperature, decreasing adsorbent particle size and pH. Adsorption of phosphate followed first-order rate kinetics. Langmuir and Freundlich adsorption isotherm constants and correlation coefficients were calculated and compared. It was concluded that the adsorption data of phosphate onto calcined alunite fitted to the Langmuir model more than Freundlich model. Specific surface areas of the calcined alunite were calculated at different calcination temperatures and particle sizes.     

粉煤灰砖块对磷酸盐的吸附特性

以建筑废料粉煤灰砖块为吸附剂材料,通过静态吸附实验研究其对磷酸盐的吸附特征,以及磷酸盐初始浓度、吸附剂投加量、pH等因素对吸附反应的影响。Langmuir、Freundlich和Temkin等温模型的分析发现,Langmuir等温式方程最适合描述吸附过程,对磷酸盐的理论饱和吸附容量为44.62 mg/g。利用伪一级动力学模型、伪二级动力学模型和颗粒内扩散模型考察了吸附过程特征,其中伪二级动力学模型为最适于描述粉煤灰砖块对磷酸盐的吸附过程的动力学模型。通过颗粒内扩散模型、Bangham方程及Boyd模型对吸附动力学机理进行的探讨表明,颗粒内扩散速率不是粉煤灰砖块吸附磷酸盐反应的惟一速率控制步,膜扩散速率和颗粒内扩散速率共同影响着吸附反应速率。磷酸盐浓度较低时主要是膜扩散限制吸附反应速率,而磷酸盐浓度较高时则颗粒内扩散成为速率控制步。研究证明,粉煤灰砖块粉末作为湿地基质具有对磷酸盐很强的吸附能力,在减少了固体废弃物的数量的同时又可以实现水污染控制的目的。     

尾矿吸附模拟废水中磷的初步研究

利用尾矿为吸附剂,模拟了其对废水中磷的去除效果.结果表明,焙烧可以明显提高尾矿对模拟废水中磷的吸附,而尾矿投加量、接触时间、pH,反应温度均是影响吸附的重要因素.热活化尾矿对磷的吸附与Langmuir、 Freundlich等温方程式的拟合程度均较高,在碱性条件下,对初始质量浓度为50mg/L的模拟含磷废水,磷的去除率可达96%以上.此外,由于尾矿具有特殊的层状结构和化学活性成分,特别是热活化尾矿,对模拟废水中的磷是较好的吸附剂,可用于去除废水中磷,是尾矿作为吸附剂去除实际废水中磷的重要基础.     

Effects of phosphate additions to soil on lead and phosphate concentrations of Holcus lanatus grown on lead amended soil

Holcus lanatus was grown in soil artificially amended with lead and phosphate. Shoot lead concentrations in the second harvest were lower where 50 mg kg⁻¹ phosphate was added to soil compared with unfertilized soil. Greater levels of fertilization did not decrease shoot lead concentrations further. The most likely mechanism was considered to be one of growth dilution and not chemical precipitation of an insoluble lead-phosphate compound in soil, as has been speculated in the past.     

改性粉煤灰净化含磷废水的研究

采用改性粉煤灰对含磷废水进行净化,考察了pH、吸附剂用量、吸附时间和吸附温度对净化效果的影响。结果表明:(1)当pH为9时,磷净化率达到最大值。(2)当改性粉煤灰用量为30g/L时,磷净化率可达99.53%,磷净化后质量浓度为0.91mg/L,达到《污水综合排放标准》(GB8978—1996)中二级标准限值(1.0mg/L);当改性粉煤灰用量为40g/L时,磷净化率可达99.75%,磷净化后质量浓度为0.48mg/L,达到GB8978—1996中一级标准限值(0.5mg/L)。(3)改性粉煤灰对废水中磷的净化速度较快,吸附5min即可使吸附过程达到平衡;进一步提高吸附时间,磷净化率及净化后浓度几乎不再变化。(4)吸附温度对磷净化率的影响较小,当吸附温度为20～40℃时,磷净化率为97.00%～98.62%。(5)改性粉煤灰对磷的吸附等温线较符合Freundlich方程,且1/n=0.374,吸附过程易进行,改性粉煤灰可作为磷的吸附剂用于废水中磷的净化。     

CPB改性沸石对磷酸盐的吸附-解吸性能研究

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性,并考察了CPB改性沸石对磷酸盐的吸附-解吸性能。结果表明,CPB改性沸石对磷酸盐具备一定的吸附能力,且吸附行为满足Langmuir等温吸附模型;粒径、改性剂投加量、反应温度、pH值及共存阴离子等因素均会影响CPB改性沸石对磷酸盐的吸附能力;减小粒径和降低反应温度均有利于CPB改性沸石对磷酸盐的吸附去除;粒径≤0.18 mm CPB改性沸石吸附磷酸盐较优的改性剂投加量为250 mmol/kg;当溶液的初始pH值位于4~10之间时CPB改性沸石对磷酸盐的吸附能力随pH值的增加而增强;SO42-的存在会明显降低CPB改性沸石对磷酸盐的吸附效率,而提高溶液的pH值有助于消除SO42-存在对CPB改性沸石吸附磷酸盐的负面影响;HCO3-的存在会一定程度上抑制CPB改性沸石对磷酸盐的吸附去除,而提高溶液的pH值无法消除HCO3-存在对CPB改性沸石吸附磷酸盐的负面影响;CPB改性沸石吸附磷酸盐后一定条件下可以重新解吸出来,且随着解吸液SO42-浓度的增加解吸率明显增大。