Nexus between polymer support and metal oxide nanoparticles in hybrid nanosorbent materials (HNMs) for sorption/desorption of target ligands

Metal oxide nanoparticles like hydrated ferric oxide (HFO) or hydrated zirconium oxide (HZrO) are excellent sorbents for environmentally significant ligands like phosphate, arsenic, or fluoride, present at trace concentrations. Since the sorption capacity is surface dependent for HFO and HZrO, nanoscale sizes offer significant enhancement in performance. However, due to their miniscule sizes, low attrition resistance, and poor durability they are unable to be used in typical plug-flow column setups. Meanwhile ion exchange resins, which have no specific affinity toward anionic ligands, are durable and chemically stable. By impregnating metal oxide nanoparticles inside a polymer support, with or without functional groups, a hybrid nanosorbent material (HNM) can be prepared. A HNM is durable, mechanically strong, and chemically stable. The functional groups of the polymeric support will affect the overall removal efficiency of the ligands exerted by the Donnan Membrane Effect. For example, the removal of arsenic by HFO or the removal of fluoride by HZrO is enhanced by using anion exchange resins. The HNM can be precisely tuned to remove one type of contaminant over another type. Also, the physical morphology of the support material, spherical bead versus ion exchange fiber, has a significant effect on kinetics of sorption and desorption. HNMs also possess dual sorption sites and are capable of removing multiple contaminants, namely, arsenate and perchlorate, concurrently.     

高氟病区茶园土壤氟形态及其分布特征

采用连续化学提取法,测定了黔西北高氟病区茶园土壤样品氟含量及氟的形态.结果表明:供试土壤全氟含量为314~3558mg/kg,平均为945mg/kg,高于全国土壤全氟平均含量(453mg/kg).不同类型供试土壤中全氟含量高低顺序为:棕壤和褐土(分别为1118和1114mg/kg)>黄棕壤(908mg/kg)>黄壤(681mg/kg).供试土壤中不同形态氟含量以残余态最高,其平均含量为940mg/kg;其次为有机束缚态氟,平均含量为7.82mg/kg,处于氟污染较高水平,可能会对人体健康和生态环境产生重要影响;铁锰结合态氟也较高,平均含量3.99mg/kg;水溶态氟和可交换态氟均较低,其平均含量分别为:1.98,1.14mg/kg.由此可见,土壤中氟形态大部分均以残余态形式存在于土壤中,可被茶树叶吸收的水溶态氟和可交换态氟含量均不高.相关性分析表明:可交换态氟只与水溶态氟呈显著正相关关系(r=0.459**),而水溶态氟与铁锰结合态氟、残余态氟和全氟均呈正相关关系(r分别为0.240*, 0.226*, 0.229*), 有机束缚态氟与铁锰结合态氟、残余态氟和全氟也呈正相关关系(r分别为0.757**, 0.312**, 0.320**),水溶态氟与土壤交换性盐基含量之间也呈极显著正相关关系,而土壤氟形态与有机质的相关性不明显,仅有机束缚态氟与土壤有机质呈弱负相关.本研究可为该区域土壤氟污染防治提供科学依据,也为土壤氟的迁移转化及其对生态和环境的影响研究奠定一定的理论基础.     

Automated indirect fluoride determination by ICP-OES using discontinuous-flow analysis

An automated method for the indirect determination of fluoride by inductively coupled plasma atomic emission spectrometry using discontinuous-flow analysis has been developed. A modified flow injection analysis system was used for sample preparation. The method is based on the determination of excess cerium(III) ion after precipitation of CeF₃. Separation of the precipitate is performed online on a syringe membrane filter that is cleaned each analysis cycle by 1 M nitric acid, ensuring a long life-time for the filter. As a result of the short reaction time, a detection limit of 9.5 mg L^?1 was obtained. The precision (RSD) of the proposed method is 1.02% at fluoride concentration of 28 mg L^?1. The applicability of the technique for groundwater monitoring of fluoride-contaminated area is demonstrated.     

Evaluation of vitamin E and calcium effects on fluoride toxicity-induced fertility impairment

Chronic fluoride (Fl) toxicity is a serious public health problem globally where drinking water contains more than 1 ppm of Fl. Sodium fluoride (NaF) produced male reproductive system toxicity. The aim of the present study was to evaluate the amelioration of Fl toxicity-induced fertility impairment by vitamin E and calcium during the withdrawal period. The study was carried out on 70 adult male albino rats divided into five main groups: group I control; subdivided into group Ia (maintained on standard diet and water ad libitum for 60 days) and group Ib (maintained on standard diet and water ad libitum for 120 days), group II was administered NaF and subdivided into group IIa (administered NaF for 60 day and sacrificed) and group IIb (administered NaF for 60 day then maintained on standard diet and water ad libitum for a further 60 days), and treated groups III, IV, and V were administered NaF. Rats were maintained during withdrawal from NaF, on vitamin E (10 mg kg^?1 day^?1 for 60 days), calcium (50 mg kg^?1 day^?1 orally for 60 days), and both vitamin E and calcium, respectively. The duration of NaF administration was 60 days at a dose 20 mg kg^?1 day^?1 for all treated groups. The following parameters were determined: body and organ weights, sperm motility, sperm morphology, sperm viability, fertility test, and hormone assays: testosterone, in vitro testosterone production, luteinizing hormone, and follicular stimulating hormone. The combined administration of vitamin E and calcium during withdrawal from NaF showed significant improvement from chronic FL-induced toxicity on male reproductive organs.     

Daily dietary fluoride intake in rural villages of the Ethiopian Rift Valley

Dental and skeletal fluorosis is widespread in the Ethiopian Rift Valley region. Drinking water has been considered the main reason for the development of fluorosis, but dietary intake may also be a contributor in areas with high concentration of fluoride in water, soil, and biota. The purpose of this study is to assess the total daily dietary fluoride intake by adults in a rural part of the Ethiopian Rift Valley. The food, beverage, and water samples were collected from selected households of three neighboring villages with similar dietary pattern, but with different fluoride content in their water sources. Village A uses water with 1.0 mg L^?1 fluoride, village B uses water with 3.0 mg L^?1 fluoride, and village C uses water with 11.5 mg L^?1 fluoride both for food preparation and for drinking. The level of fluoride was determined in all food ingredients, in the prepared food, beverages, and in the water used for food preparation and drinking. Recipe and food frequency questionnaires were used to gather household food preparation and consumption patterns. An alkali fusion method was used for digestion of food samples and for subsequent determination of fluoride with ion-selective electrode. The daily fluoride intake varied depending on its concentration in the water used for cooking and drinking. In households using water with 1 mg L^?1, 3 mg L^?1, and 11.5 mg L^?1 fluoride, the total personal intake was found to be 10.5, 16.6, and 35.3 mg d^?1, respectively. Contribution of the water to the daily fluoride intake was 33%, 58%, and 86%, respectively. Even in households using water containing fluoride at a concentration of 1 mg L^?1, the daily intake was higher than the recommended safe intake of 1.5–4.0 mg d^?1 for adults, which indicates that the fluoride intake through food may cause health risks. Minimizing the fluoride concentration in water to the lowest possible level will greatly reduce the daily intake. The form of fluorine (organic or inorganic) in the food items and the associated health risk factors need further investigation.     

氟离子慢性暴露对中国林蛙蝌蚪生长发育的毒性效应研究

氟元素以不同的结合形式广泛存在于自然界中,适量氟的摄取有益于龋齿预防和骨骼发育,然而过量氟的摄取会对动物及人体健康造成危害。近年来,大量的人类活动导致水环境中氟含量持续升高。为探究水域氟污染对中国林蛙的毒性影响,本研究以中国林蛙(Rana chensinensis)胚胎为试验材料,对卵黄栓期(G12期)胚胎进行了0、0.7、4.2、19.4、42.8 mg·L~(-1)F-慢性水体暴露直至胚胎发育到变态高峰期(G42期)的研究。分别于暴露25 d和40 d后取样测定了蝌蚪全长、体长、体重和发育分期;此外,分析了F-慢性暴露对变态率、G42期蝌蚪的全长、体长、体重和后肢长以及G42期蝌蚪骨骼发育的影响。结果表明:暴露25 d时,4.2 mg·L~(-1)F-处理组促进了林蛙蝌蚪的生长发育,而42.8 mg·L~(-1)F-处理组显著抑制了蝌蚪的生长发育;暴露40 d时,19.4 mg·L~(-1)F-和42.8 mg·L~(-1)F-处理组蝌蚪的生长发育均受到显著抑制。持续进行慢性暴露78 d后,4.2 mg·L~(-1)F-处理组蝌蚪的变态率显著升高,而42.8 mg·L~(-1)F-处理组蝌蚪的变态率受到了显著抑制。此外,42.8 mg·L~(-1)F-处理组G42期蝌蚪形态指标(全长、体长和后肢长)以及骨骼发育均受到抑制。依据G42期中国林蛙蝌蚪的生长发育指标和变态率为观察指标,氟离子慢性暴露对中国林蛙蝌蚪的最低可观察效应浓度(LOEC)为0.7 mg·L~(-1)。研究表明,水环境中高浓度的氟污染会对中国林蛙蝌蚪的生长发育、变态和骨骼发育等造成潜在的不利影响,水体氟污染的生态毒性效应理应引起高度重视。     

上海市土壤氟含量风险管控限值探讨

受工业活动影响,上海市典型工业区表层土壤氟中位值普遍高于"七五"背景值。针对工业企业场地土壤氟化物高值现象,目前仍缺乏相关的管理标准体系,且基于总量的评估分析方法已无法满足日益增长的精细化管理需求。详细梳理了国内外氟化物相关标准体系,并对上海市土壤氟限值进行了探讨。基于上海市典型工业场地特征参数计算得到的土壤氟化物筛选值高于上海市土壤"七五"背景值,与上海市工业场地调查得到的土壤氟化物高值基本持平;第一类、第二类用地的氟化物筛选建议值分别为1 980、10 000 mg/kg。与氟化物相比,水溶态氟化物是影响作物体内氟含量的重要因素,且在淋溶等作用下会对地下水安全构成威胁。考虑到水溶态氟化物的环境行为与风险,建议针对农田土壤开展水溶性氟化物含量限值研究。     

pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

安徽茶园土壤氟在茶树体内的富集与转运特征

研究了安徽宣城、六安和合肥茶区不同茶园土壤氟含量及在茶树体内的富集与转运特征,探讨了茶树根际和非根际土壤氟的有效性特征及其在茶树体内的累积规律.结果表明,安徽省典型茶园表层土壤全氟含量为：六安黄棕壤（319.7 mg.kg^-1）〉宣城黄红壤（316.6 mg.kg^-1）〉合肥黄褐土（311.3 mg.kg^-1）,...     

亳州中药材及产地土壤和地下水中氟化物含量

分析了毫州典型中药材及产地土壤和地下水中氟化物的含量.结果表明,中药材基地表层土壤全氟平均和水溶性氟含量分别在278.4-625.6 mg·kg-1和5.02-16.3 mg·kg-1之间,均值分别为532.8 mg·kg-1和9.88 mg·kg-1.表层土壤全氟平均含量高于全国土壤总氟背景值(478 mg·kg-1...