Groundwater quality in the major industrial area of Thessaloniki,Greece part 1: Chemical composition‐geochemical processes

Adsorption rates of Sb(V) ions on an activated alumina (AA) were analyzed by batchwise experiments, while the continuous adsorption, desorption, regeneration of AA, and multiple reuse cycles were studied by flow column tests. The adsorption rates increased quickly with the increases of shaking speed and operation temperature. The adsorbed Sb(V) ions were desorbed easily by a 50 mM NaOH solution, and a 41–90 times concentrated Sb(V) solution was yielded correspondingly. AA was effectively regenerated by desorption operation and ca. 93% of the initial adsorption capacity was retained after six times adsorption/desorption cycles.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

Removal of As(V) and Sb(V) in aqueous solution by Mg/Al-layered double hydroxide-incorporated polyethersulfone polymer beads (PES-LDH)

To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1–2 mm. On the PES-LDH surface, nanosized CLDH (100–150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.

     

武汉月湖水体主要元素与浮游植物的PCA与CCA分析

通过2007年1—12月对武汉月湖不同的取样点进行监测,并选择汉江琴台段水域作为研究对照,调查了月湖水体硅藻、蓝藻与水体主要元素的种类,采用PCA、CCA分析法探讨了月湖水体硅藻、蓝藻与水体元素种类的关系。结果表明:月湖水体中所含元素全年监测出28种;汉江琴台段水域中所含元素全年监测出27种。经PCA分析表明,月湖水体中累计贡献率较大为磷(P)、砷(As)、铁(Fe)、铜(Cu)、锰(Mn);汉江琴台段水域累计贡献率较大为硅(Si)、锑(Sb)、镉(Cd)、钒(V)、钡(Ba)、Ag(银)、钼(Mo)。月湖水体中蓝藻密度大于硅藻,汉江琴台段水域硅藻密度大于蓝藻。经CCA分析表明,月湖硅藻密度与硒(Se)、锶(Sr)、银(Ag)、Ba、铝(Al)呈正相关关系;月湖蓝藻密度与P、Cu、铬(Cr)呈正相关关系,月湖蓝藻密度与镁(Mg)、镍(Ni)、钙(Ca)、锌(Zn)、硫(S)呈负相关关系。CCA分析中,汉江琴台段硅藻密度与铅(Pb)、硼(B)、As、Cr、Zn、Al、Cu、Mn、Fe、P呈负相关关系,汉江琴台段硅藻密度与Mo、Ca、钴(Co)、V、Sr、Ag呈正相关关系;汉江琴台段蓝藻密度与钠(Na)、S、Mg、Ni、钾(K)呈负相关关系。月湖水体缺乏可溶硅(dissolved silicon,DSi),硅藻会提升对其他元素(Se、Sr、Ag、Ba、Al)的吸收能力,这些元素会起到缺乏元素(Si)近似的作用,替代性可能出现。水中各种元素的组态是导致月湖浮游植物群落发生演变的重要原因之一。     

Comparison of masking agents for antimony speciation analysis using hydride generation atomic fluorescence spectrometry

A sensitive atomic spectrometric method for the redox speciation analysis of Sb in water is described. The proposed method is based on the selective generation of stibine from Sb(III) in a continuous flow system using non-dispersive atomic fluorescence spectrometry for detection. The effects of the HCl concentration on the fluorescence intensities of Sb(III) and Sb(V) were investigated. The results indicated that atomic fluorescence emission due to Sb(V) can constructively interfere with the determination of Sb(III). For the determination of Sb(III), four compounds were tested as masking agents to inhibit the generation of stibine from Sb(V). The effects of the concentrations of the masking agents and of HCl on the fluorescence signals from Sb(III) and Sb(V) were studied. The results indicated that citric acid and NaF can successfully suppress hydride generation from Sb(V). To evaluate the developed methodology and the influence of the matrix, the recovery of Sb(III) from natural water that was spiked with different Sb(III) and Sb(V) concentrations was tested.     

Removal of arsenate from water by adsorbents: a comparative case study

Laboratory and field filtration experiments were conducted to study the effectiveness of As(V) removal for five types of adsorbent media. The media included activated alumina (AA), modified activated alumina (MAA), granular ferric hydroxide (GFH), granular ferric oxide (GFO), and granular titanium dioxide (TiO?). In laboratory batch and column experiments, the synthetic challenge water was used to evaluate the effectiveness for five adsorbents. The results of the batch experiments showed that the As(V) adsorption decreased as follows at pH 6.5: TiO? > GFO > GFH > MAA > AA. At pH 8.5, however, As(V) removal decreased in the following order: GFO = TiO? > GFH > MAA > AA. In column experiments, at pH 6.5, the adsorbed As(V) for adsorbents followed the order: TiO? > GFO > GFH, whereas at pH 8.5 the order became: GFO = TiO? > GFH when the challenge water containing 50 μg/L of As(V) was used. Field filtration experiments were carried out in parallel at a wellhead in New Jersey. Before the effluent arsenic concentration increased to 10 μg/L, approximately 58,000 and 41,500 bed volumes of groundwater containing an average of 47 μg/L of As(V) were treated by the filter system packed with GFO and TiO?, respectively. The As(V) adsorption decreased in the following sequence: GFO > TiO? > GFH > MAA > AA. Filtration results demonstrated that GFO and TiO? adsorbents could be used as media in small community filtration systems for As(V) removal.     

Enhancement of As(V) adsorption onto activated sludge by methylation treatment

Biosorption properties of arsenate [As(V)] onto activated sludge were investigated in batch systems. The adsorption of As(V) onto sludge increased from 23 to 266 μg/g dry weight through the methylation of the activated sludge. This increase resulted from neutralization of carboxylic groups via the methylation process. The pH effect of As(V) uptake was also investigated and As(V) adsorption by methylated sludge decreased significantly at high pH (pH > 11) due to competition between As(V) and OH⁻ ions for binding sites distributed on sludge surfaces. In contrast, low pH favored As(V) adsorption by methylated sludge because of the elevated quantities of positively charged functional groups. The results suggest that methylated activated sludge may provide promising applications for the simultaneous removal and separation of As(V) from aqueous effluents.     

石英砂负载氧化铁吸附除锑的研究

考察了石英砂负载氧化铁(IOCS)在不同的实验条件下(无机阴离子种类及其离子强度、 pH值、IOCS投加量、温度等)对水溶液中锑的去除效果.结果表明:三种无机阴离子(NO-3,Cl-,SO2-4)对IOCS吸附锑的去除率、吸附容量以及反应速率几乎没有影响;在pH3-9范围内,锑的去除率达到90%.二级反应动力学模型及Langmuir等温吸附模型可分别较好地描述锑的吸附动力学及吸附等温线实验结果.随着温度的增加,反应速率以及吸附容量也随之增加.     

Removal of arsenate from water by adsorbents: a comparative case study

Laboratory and field filtration experiments were conducted to study the effectiveness of As(V) removal for five types of adsorbent media. The media included activated alumina (AA), modified activated alumina (MAA), granular ferric hydroxide (GFH), granular ferric oxide (GFO), and granular titanium dioxide (TiO₂). In laboratory batch and column experiments, the synthetic challenge water was used to evaluate the effectiveness for five adsorbents. The results of the batch experiments showed that the As(V) adsorption decreased as follows at pH 6.5: TiO₂ > GFO > GFH > MAA > AA. At pH 8.5, however, As(V) removal decreased in the following order: GFO = TiO₂ > GFH > MAA > AA. In column experiments, at pH 6.5, the adsorbed As(V) for adsorbents followed the order: TiO₂ > GFO > GFH, whereas at pH 8.5 the order became: GFO = TiO₂ > GFH when the challenge water containing 50 μg/L of As(V) was used. Field filtration experiments were carried out in parallel at a wellhead in New Jersey. Before the effluent arsenic concentration increased to 10 μg/L, approximately 58,000 and 41,500 bed volumes of groundwater containing an average of 47 μg/L of As(V) were treated by the filter system packed with GFO and TiO₂, respectively. The As(V) adsorption decreased in the following sequence: GFO > TiO₂ > GFH > MAA > AA. Filtration results demonstrated that GFO and TiO₂ adsorbents could be used as media in small community filtration systems for As(V) removal.     

Recent advances in antimony removal using carbon-based nanomaterials: A review

• The synthesis and physicochemical properties of various CNMs are reviewed. • Sb removal using carbon-based nano-adsorbents and membranes are summarized. • Details on adsorption behavior and mechanisms of Sb uptake by CNMs are discussed. • Challenges and future prospects for rational design of advanced CNMs are provided. Recently, special attention has been deserved to environmental risks of antimony (Sb) element that is of highly physiologic toxicity to human. Conventional coagulation and ion exchange methods for Sb removal are faced with challenges of low efficiency, high cost and secondary pollution. Adsorption based on carbon nanomaterials (CNMs; e.g., carbon nanotubes, graphene, graphene oxide, reduced graphene oxide and their derivatives) may provide effective alternative because the CNMs have high surface area, rich surface chemistry and high stability. In particular, good conductivity makes it possible to create linkage between adsorption and electrochemistry, thereby the synergistic interaction will be expected for enhanced Sb removal. This review article summarizes the state of art on Sb removal using CNMs with the form of nano-adsorbents and/or filtration membranes. In details, procedures of synthesis and functionalization of different forms of CNMs were reviewed. Next, adsorption behavior and the underlying mechanisms toward Sb removal using various CNMs were presented as resulting from a retrospective analysis of literatures. Last, we prospect the needs for mass production and regeneration of CNMs adsorbents using more affordable precursors and objective assessment of environmental impacts in future studies.     

Antimony speciation and contamination of waters in the Xikuangshan antimony mining and smelting area,China

Water samples from Xikuangshan (China), the world largest antimony (Sb) mine with a Sb mining and smelting history of more than 200 years, were analyzed. These water samples ranged from stream water in the vicinity of the mining and smelting area that received seepage from ore residues to the underground mine-pit drainage. The concentrations of total Sb, Sb (III) and Sb (V) of the samples were determined by HPLC-ICP-MS. In addition, water pH and concentrations of major cations and anions were analyzed. All 18 samples demonstrated total Sb concentrations with ppm levels from 0.33 ppm to 11.4 ppm, which is two to three orders of magnitude higher compared to the typical concentration of dissolved Sb in unpolluted rivers (less than 1 ppb). This is probably the first time that such high Sb contents have been documented with complete environmental information. Distribution of total Sb and Sb species was investigated, taking into account the respective local environment (in the mining area or close to the smelter, etc.). Sb (V) was the predominant valence in all 18 samples. Only trace levels of Sb (III) were detected in 4 of the 18 samples. Geochemical speciation modeling showed the dominant species was Sb(OH)₆⁻. It is also probably the first time that such high Sb contents have been documented in the natural environment with Sb speciation distribution information. Several potential oxidation pathways are also discussed that might have facilitated the oxidation of Sb (III) in the natural environment. Signs of intoxication were observed among local mine workers with extensive exposure to different forms of Sb for a long period of time.     

南京城市土壤重金属含量及空间分布特征

研究了南京城市土壤重金属含量、来源及空间分布特征。结果表明,南京城市土壤中V、Mn、Co、Ni、Cr污染不明显,但受到了不同程度的Cu、Pb、Zn、Sb、Hg、Cd污染,其中Hg污染比较严重。V、Mn、Co、Ni、Cr含量之间均呈极显著正相父;Cu、Pb、Zn、Sb、Hg、Cd含量之间也均呈极显著正相关。南京城市土壤V、Mn、Co、Ni、Cr主要继承了原土物质;Hg、Cd、Pb主要来源于城市燃煤、机动车尾气及工厂排放粉尘;Sb主要来源于机动车尾气和工厂排放粉尘。南京城市土壤Hg、Cd、Pb、Sb含量空间分布规律非常相似,均表现为外围向市中心有逐渐增加的趋势,并且在新街口—鼓楼、梅山硫铁矿形成异常高值的岛状、环状区域。     

Antimony (Sb) – pollution and removal techniques – critical assessment of technologies

In view of increasing emissions of antimony (Sb) into the environment due to industrialization and consequent carcinogenicity, it is essential to remove this metal from the ecosystem. Antimony and arsenic (As) are analogs. Although numerous studies examined arsenic removal, few reports are available on Sb removal. In this review, various Sb removal techniques are described to understand how this process occurs and what research gaps are needed to improve efficiency. At present, surface adsorption technique is the most widely used for Sb removal. Biological treatment namely phytoremediation is also a promising method and more investigations are required in this regard. The selection of a suitable technique for a given area depends on the conditions including economic, environmental, and social conditions.     

Copper(II) ions’ removal from aqueous solution using green horse-chestnut shell as a low-cost adsorbent

The adsorption of copper(II) ions from aqueous solutions by the green horse-chestnut shell was studied in a batch adsorption system. It was determined how the parameters of the adsorption process, such as time, pH, copper(II) ions concentration and sorbent dose, influence the effectiveness of copper(II) ions’ removal. The adsorption process was fast and equilibrium was established about 10?min, and near 95–97% of Cu(II) ions were removed from aqueous solution. Maximum copper(II) ions’ adsorption occurred at around pH 5. The adsorption kinetics are also described, using pseudo-first-order model and pseudo-second-order model of type 1 and 2. A comparison of the kinetics models on the overall adsorption rate showed that the adsorption system was best described by the pseudo-second-order model of type 1 (r²?=?0.999) for all initial concentrations. Another key part of this study was the use of the Freundlich model to determine the adsorption isotherm and the experimental data were in strong correspondence with this model.     

Tissue distribution of antimony (Sb) in piglets orally given graded levels of Sb (V)

The potential risks from oral intake of soil antimony (Sb) depends mainly on the amount of metal ingested and its bioavailability. Relative bioavailability may be determined by comparing Sb present in soil to a reference compound, taking into account accumulation in different target tissues or excretion. However, due to the lack of scientific knowledge concerning the fate of Sb in the organism, there is a need to study the absorption and distribution of Sb in order to select target tissues for assessment of bioavailability of Sb in soils. Thus, 45 piglets were exposed to a soluble pentavalent antimony salt (KSb(OH)₆), for 15 days at concentrations ranging from 0–1600 µg Sb/kg body weight (BW) per day. Following the exposure period, blood, plasma, liver, spleen, kidneys, hair, bone, bile and urine were obtained to measure Sb concentrations by ICP-MS. Results showed that tissue Sb levels were dose-related. Higher Sb concentrations were found in urine, kidneys, hair, bone and liver. Sb(V) was not detectable in blood and plasma. In the case of highly contaminated soil with soluble forms of Sb in concentrations ranging from 200–1600 µg Sb/kg BW, kidneys, liver and spleen are the most reliable compartments to determine Sb bioavailability from soil. However, for the soils with lower levels of contamination and a low Sb bioaccessibility, urine may serve as a relevant compartment.     

胶团强化超滤中SDS胶团与镉离子的吸附特性

以十二烷基硫酸钠(SDS)作为表面活性剂,对含有Cd2 的水溶液进行胶团强化超滤分离.考察胶团强化超滤中表面活性剂与镉离子比值对镉离子吸附总量、截留率的影响,以及胶团与镉离子的吸附等温规律和吸附动力学规律,并对吸附机理进行了初步探讨.实验结果表明:Cd2 截留率可以达到97%以上,SDS与镉离子的吸附过程符合Langmuir吸附等温方程,并遵循Lagergren二级动力学规律,其吸附作用主要是化学吸附.     

Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane: effects of arsenic concentration, pH, and co-existing ions

A laboratory-scale investigation was performed to study arsenic (As (V)) removal by negatively charged GE-HL nanofiltration (NF) membrane in simulated drinking water. Effects of As (V) concentration (0–200 μg·L^?1), pH, and co-ions and counter-ions were investigated. The NF membrane presented good stability, and the rejection rates exceeded 90%. The rejection rates of As (V) decreased with the increase of As (V) concentration, while it increased with the increase of pH (reached 96% at pH 6.75). Moreover, a negative relationship was observed between the co-existing ions of Cl^?, Na⁺, SO ₄ ^2? , and Ca²⁺ and the removal of As (V), in which bivalent ions presented more significant effects than monovalent ions.     

土壤中常见离子在紫外区的吸收特性──Ⅱ.高浓度离子溶液与低浓度混合

探讨不同离子浓度与不同无机溶液的混合对紫外光吸收的影响,结果表明,盐酸盐在较高浓度下吸收值迅速增大,吸收峰向红区移动,而硫酸盐在远紫区有一定程度的吸收,KH2PO4与NH4F接近无吸收。多数情况下,无机溶液对紫外光的吸收主要决定于阴离子类型,而与阳离子无关.不同类型溶液的混合基本不改变溶液的吸收特性,硝酸盐在低浓度下对紫外的吸收极为稳定,基本不受共存离子的干扰。0.01mol/LCuSO4与2mol/LKCI吸收峰与硝酸盐吸收峰重叠,但饱和CaSO4与硝酸盐吸收峰不重叠。     

Arsenic adsorption on lignocellulosic substrate loaded with ferric ion

We loaded a lignocellulosic substrate extracted from wheat bran with ferric ions. This new low-cost adsorbent was prepared for the adsorption and removal of arsenate and arsenite ions from aqueous systems. The loading process of Fe in this biomaterial was done by hydrolization of a ferric salt while an alkaline solution was added dropwise. The new material obtained has a high sensivity to arsenite and arsenate species. Here, we investigated the effect of contact time, pH, and Fe content on the adsorption of both arsenic ions on the new material. This adsorption was found to be highly pH-dependent, which can be explained on the basis of electrostatic interactions between ionic species in solution and the ≡FeOH surface groups. The maximum adsorption capacity of arsenite and arsenate species vary linearly with the amount of Fe loaded on the lignocellulosic substrate.     

Improved characterisation of inorganic components in airborne particulate matter

We set up a microanalytical procedure for non-volatile ions by ion chromatography (IC) and for elements by energy-dispersive X-ray fluorescence (ED-XRF) and inductively coupled plasma optical emission spectroscopy (ICP-OES). We analysed NO₃, SO₄, NH₄, Na, Mg, Ca, Fe, S, Zn, As, Cd, Cu, Mn, Ni, Pb, Sb, Se, Ti, and V. The use of complementary techniques yields reliable data for both trace and crustal elements, overcoming the analytical restrictions characteristic of the individual techniques. Some elements determined by two or by all three techniques can be used as data quality markers. The application of the procedure to a short PM_2.5 monitoring campaign is also described, aimed to the identification of fireworks tracers.