磷石膏水热法合成硫酸钙晶须

以磷石膏为原料，二水合硫酸钙、硫酸镁、甘油为添加剂，采用水热法合成硫酸钙晶须，考察了料浆含量、反应温度、反应时间、体系pH等因素对晶须的直径和长径比的影响；并采用SEM技术观察硫酸钙晶须的形貌。实验结果表明，当磷石膏含量2.5%（w）、反应温度130 ℃、反应时间4 h、体系pH 4时，制备得到的硫酸钙晶须长径比为56.24，平均直径为0.17 μm。SEM表征结果显示，硫酸钙晶须形貌规整、分散均匀、直径较小，达百纳米级。     

Releases of phosphate fertilizer industry in the surrounding environment: Investigation on heavy metals and polonium-210 in soil

Distribution of Cu,Zn,Pb,Cr,Ni,Mn concentrations and the activity of polonium-210 in the surrounding area of a phosphate fertilizer industry located on the eastern coast of the Mediterranean Sea has been determined.Nineteen sampling sites were distributed around the industrial zone on a surface area of about 100,000 m2.Atomic absorption spectroscopy and Alpha spectroscopy were used to quantify the heavy elements and polonium-210,respectively.Investigation on a particle scale was conducted by TEM and SEM coupled to EDX and X-ray cartography to determine the nature of heavy elements carriers and their distribution.Heavy elements were mainly concentrated inside the particle size fraction 50 μm.Their levels decreased with distance increasing from the industry.According to the reference soil,enrichment factors were about 10,15,32 and 100 times for Zn,Pb,Cu,and Cr,respectively inside the particle size fraction 50 μm on the closest sites to the industry.The main contaminant sources were transport and storage of row materials and the free release of phosphogypsum waste.Heavy elements were entrapped inside agglomerates of sulfates,phosphates and iron oxihydroxides in a di used shape.Polonium-210 with an enrichment factor of about 56,showed the same behavior of the spatial distribution of the trace elements.     

磷石膏改良基质中As和F在蔬菜内富集和迁移特征

为了查明改良磷石膏是否可作为农作物耕种地,选取白菜、菠菜、叶用芥菜和上海青种植在改良磷石膏基质上,分析了As和F在四种蔬菜中的富集及迁移特征。结果表明:As和F在蔬菜中的含量范围分别为0.27～1.56mg/kg、79.14～265.65mg/kg,均超过《农产品安全质量无公害蔬菜安全要求》。As和F在蔬菜中的富集系数分别为0.07～0.25、0.23～0.44。叶用芥菜和白菜地下部位中As和F迁移显著,而上海青和白菜地上部位中As和F迁移显著。总体而言,As在蔬菜中迁移规律表现为地下部位>地上部位,F在蔬菜中迁移规律表现为地上部位>地下部位。改良后的磷石膏不适宜于种植蔬菜。     

磷石膏制硫酸钾中试研究

以湿法磷酸副产的磷石膏和工业品氯化钾为原料 ,采用两步法 ,常温常压下 ,在 5 0 0 0t a工业化装置中 ,生产符合国标ZBG2 10 0 6 89农用一级品硫酸钾。整个过程流程较简单 ,能耗低 ,投资省 ,基本无“三废”排放。钾的收率达70 %。工艺条件稳定 ,产品质量稳定。中试结果与小试有较好的重复性 ,放大效果好。     

施用磷石膏对碱化土壤氟含量及其吸附特性的影响

通过室内培养试验和田间试验就施用磷石膏对土壤氟含量和土壤对氟吸附特性的影响进行了研究．结果表明，经连续４年施用磷石膏改良土壤后，０—２０ｃｍ土层全氟积累现象明显．但是，土壤水溶性氟含量却随磷石膏施用量增加而降低．土壤对氟的吸附数据均能与Ｌａｎｇｍｕｉｒ，Ｆｒｅｕｎｄｉｌｉｃｈ和Ｔｅｍｋｉｎ方程很好地拟合，施用磷石膏处理土壤对氟的最大吸附量高于没有施用磷石膏处理的．影响土壤水溶性氟含量和吸附特性的主要因素可能是土壤钙含量的增加和ｐＨ值的降低．     

以废渣磷石膏为原料水热法制备硫酸钙晶须

以磷石膏为原料,采用水热法制备硫酸钙晶须。借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)及红外光谱仪(FT-IR)等仪器对产物进行表征,研究了反应温度和时间、料浆初始固液比及不同添加剂等因素对产物形貌及可溶磷含量等的影响。结果表明,最佳反应条件为:反应温度140℃,反应时间2 h,料浆固液比为1∶10,最佳添加剂及剂量为丙三醇(V醇/V总液为50%)。所得产物为六方晶系的CaSO4.0.5H2O,直径1～3μm,晶须长径比为45左右,合成率约95%,产物可溶磷含量由原样的0.41%降至0.21%。     

硫酸钙晶须对磷的静态吸附

以磷石膏废渣为原料制备硫酸钙晶须，考察了硫酸钙晶须对模拟含磷废水中磷的去除效果，分析了初始废水pH、初始磷质量浓度、硫酸钙晶须加入量对磷吸附效果的影响，研究了硫酸钙晶须对磷的吸附等温线，同时对吸附机理进行了探讨。实验结果表明：硫酸钙晶须在碱性条件下对磷的去除率较酸性条件下高，且初始废水pH为10时去除效果最佳;最佳硫酸钙晶须加入量为0.03 g/mg（以磷计）;在初始废水pH为10、初始磷质量浓度为50 mg/L、硫酸钙晶须加入量为1.5 g/L的条件下，于25 ℃下反应1 h，磷的去除率达到99.16%，上清液TP为0.419 mg/L;与Freundlich模型相比，Langmuir等温吸附模型更适合描述硫酸钙晶须对磷的吸附过程，采用该模型拟合得出25 ℃下磷的饱和吸附量为140.4 mg/g。     

Morpho-histological and enzymatic alterations in earthworms Drawida willsi and Lampito mauritii exposed to urea,phosphogypsum and paper mill sludge

The effects of varying concentrations of urea, phosphogypsum and paper mill sludge (PMS) on the morphology, histology, tissue protein content, lipid peroxidation (LPX), activities of lactate dehydrogenase (LDH), acetylcholinesterase (AChE) and catalase in earthworms Drawida willsi and Lampito mauritii have been studied over an exposure period of 24?hr. Integumentary lesions, clitellar swelling and loss of pigmentations were found to be major morpho-pathological changes in the worms. Histology indicated cuticular damage, ruptured epithelium and muscle fibres with accumulation of cellular debris. Lowest tissue protein content (57.02?±?4.02?mg/g tissue) and highest LPX (0.113?±?0.04, 0.137?±?0.08?nmol/mg protein) were noticed in D. willsi at a high concentration of PMS, whereas highest tissue protein content was observed in L. mauritii (115.32?±?7.18?mg/g tissue) with the same treatment. In both the species, LDH activity was minimum at a high concentration of urea (0.172?±?0.02; 0.247?±?0.08?U/mg protein). AChE activity was highest (0.099?±?0.002?U/mg protein) at a high concentration of PMS in D. willsi, whereas catalase activity was the maximum (0.338?±?0.02?U/mg protein) at high concentrations of PMS in L. mauritii. The study indicated that morpho-histological and enzymatic alterations in these earthworms exposed to agrochemicals could be useful biomarkers to evaluate soil toxicity.     

磷石膏浸出液对斑马鱼的急性毒性及氧化应激损伤

以斑马鱼（Danio rerio）为受试鱼种,研究了磷石膏浸出液对水生生物的急性毒性及亚致死浓度下对斑马鱼肝脏、肌肉和鳃中超氧化物歧化酶（SOD）、过氧化氢酶（CAT）、谷胱甘肽过氧化物酶（GPx）和丙二醛（MDA）的影响,以及96 h后肝脏和鳃组织病理变化.结果表明,磷石膏浸出液中总磷、氟化物和Cd、Cr、Pb、Hg浓度超出地表水V类水标准,其对斑马鱼的毒性较强,96 h半数致死浓度（LC₅₀）为6.5%（体积分数）.慢性毒性实验显示,随暴露时间延长,各组织内3种抗氧化酶活性变化趋势不完全一致,但高浓度（0.65%和3.25%）暴露后期（72 h和96 h）几乎均受到显著抑制,其中,SOD对浸出液的敏感性最高;MDA含量变化规律较为一致,随浸出液浓度增加而升高,肝脏、肌肉和鳃中MDA最高含量均出现在72 h,分别是空白对照组的1.8、1.6和2.1倍,至96 h时略有降低,但仍显著高于对照组.各浓度组暴露96 h后,肝细胞窦间隙扩大,肝巨噬细胞增多,细胞核固缩,部分细胞质空泡化,组织水肿;鳃组织出现上皮细胞增生、脱落,鳃丝充血,鳃小片弯曲变形等现象.综上,未加处理的磷石膏浸出液已超出斑马鱼耐受极限,任其排入环境具有潜在的生态风险.     

山谷型磷石膏渣场酸性工艺水渗漏分析

我国大多数磷石膏渣场建于山谷之中,并以黏土底垫层作为防渗层。通过建立针对典型山谷型磷石膏渣场的渗流模型,使用二维有限元渗流分析方法对山谷型磷石膏渣场酸性工艺水的渗漏模式和渗漏量进行了分析。分析表明:山谷型磷石膏渣场酸性工艺水渗漏量不仅和黏土防渗层的垂直渗透系数有关,而且与黏土防渗层下部风化岩层的水平渗透性相关。如水平渗透性较大,黏土防渗层对阻止酸性工艺水流失的作用有限。分析还表明,由于谷口垂直防渗帷幕不大可能封堵住所有风化岩层中的裂隙,很难阻止渗过黏土防渗层的酸性工艺水向渣场外渗漏。