Phosphorus sorption and recovery using mineral-based materials: Sorption mechanisms and potential phytoavailability

Recovery and re-use of P within hitherto unexploited waste streams may serve to reduce pressure on limited phosphate rock reserves. Since the mid-20th century there has been a dramatic increase in the use of mined phosphate rock for food production. Although economically exploitable quantities of phosphate rock are found in several countries, food security in those areas without domestic phosphate rock reserves is potentially vulnerable. Development and utilisation of efficient, cost-effective techniques for P recovery from solid and liquid waste materials may also reduce energy and/or material requirements for P acquisition. Phosphorus may be removed from solution via selective sorption to a solid phase and direct use of the material as a fertilizer or soil conditioner, or the sorbed P may subsequently be stripped from the solid sorbent and chemically precipitated as a high-purity fertilizer. Ideal sorbents for P recovery from solution possess high phosphate sorption capacity and selectivity, are capable of kinetically rapid P sorption from solution, and are stable materials resistant to degradation during both P sorption and desorption. This review provides a critical assessment of P sorption to a range of mineral-based materials and the potential application of these materials to P recovery schemes.     

内蒙古地质地球化学分区及地球化学成矿预测

通过内蒙古表生环境中元素相容性排序检验,认为1∶20区域化探普查成果能提供原生环境中各类地质信息,尤其是普查找矿信息。区域化探元素测试结果存在系统误差,通过数据调平处理,保证了化探数据的质量。ln(wCr×wNi×wCo)等图件提供的信息,可作为划分地质地球化学分区的主要依据之一,对基础地质研究有参考价值。在此基础上初步圈定了元素地球化学成矿预测区,为内蒙古自治区提供了有价值的普查找矿信息。     

我国硫资源供需状况及需求预测

全球硫资源特征及国内硫资源供需现状表明,国内硫资源贫乏,硫资源生产与消费逐年增加,尤其磷肥生产对硫资源的需求越来越迫切,预计到2020~2025年磷肥用硫量将达到峰值1620万t左右,不包括出口磷肥耗硫量。因此,加强硫资源的综合利用、加大硫铁矿找矿及矿山设计是非常有必要的。     

Residence and redistribution of REE, Y, Zr, Th and U during granulite-facies metamorphism: behaviour of accessory and major phases in peraluminous granulites of central Spain

Accessory minerals are thought to play a key role in controlling the behaviour of certain trace elements such as REE, Y, Zr, Th and U during crustal melting processes under high-grade metamorphic conditions. Although this is probably the case at middle crustal levels, when a comparison is made with granulite-facies lower crustal levels, differences are seen in trace element behaviour between accessory minerals and some major phases. Such a comparison can be made in Central Spain where two granulite-facies terranes have equilibrated under slightly different metamorphic conditions and where lower crustal xenoliths are also found. Differences in texture and chemical composition between accessory phases found in leucosomes and leucogranites and those of melanosomes and protholiths indicate that most of the accessory minerals in melt-rich migmatites are newly crystallized. This implies that an important redistribution of trace elements occurs during the early stages of granulite-facies metamorphism. In addition, the textural position of the accessory minerals with respect to the major phases is crucial in the redistribution of trace elements when melting proceeds via biotite dehydration melting reactions. In granulitic xenoliths from lower crustal levels, the situation seems to be different, as major minerals show high concentration of certain trace elements, the distribution of which is thus controlled by reactions involving final consumption of Al-Ti-phlogopite. A marked redistribution of HREE–Y–Zr between garnet and xenotime (where present) and zircon, but also of LREE between feldspars (K-feldspar and plagioclase) and monazite, is suggested.     

葡萄微肥"双增灵"优质丰产试验

在砀山酥梨微肥"酥梨宝"优质增产试验的基础上,通过对"酥梨宝"微肥配方的适当调整,重新配制出葡萄微肥"双增灵",在我省著名的葡萄产地萧县龙山和淮北市大庄两地,同时进行酿酒和鲜食品种的优质丰产试验.叶面肥试验表明:鲜食品种巨峰可溶性固形物平均增加1.97%,增幅达15%,总糖平均增加0.78%,增幅6%,维生素C平均增加1.259mg/100g,增幅达18%;酿酒品种白羽总糖平均增加0.59%,增幅5%,维生素C平均增加0.33mg/100g,增幅5%,产量平均提高5.07kg/株,增幅高达26.5%.同时,试验的葡萄果实中,对人体十分有益的硒(4～24倍)、锌(约1倍)元素含量也有了大幅度的提高.     

Effect of contact time,pH, and ionic strength on Cd(II) adsorption from aqueous solution onto bentonite from Gaomiaozi,China

Copper smelting and toxic emissions in Sarcheshmeh Copper Complex have resulted in soil pollution especially in the vicinity of the smelting plant. Calculated geoaccumulation index, contamination factor (C _f), and contamination degree (C _deg) indicate surface soil enrichment in potentially toxic metals (As, Cu, Pb, Zn, Mo, and Cd). The results also indicate that most contaminated areas are located in the prevailing wind directions (N and NE). However, continuous copper smelting can result in extensive pollution in the study area. This is especially alarming for adjacent townships. Since, the sampled sites are also used as grazing land, the soils are likely to become phytotoxic and provide a potential pathway for the toxic elements to enter the food chain. C _f based on distance and direction give more reasonable results; that is, the decrease of contamination degree with distance. This is in agreement with I _geo and also statistical analysis, which show a decreasing trend of metal loadings of soil with distance from the smelter. Statistical analysis reaffirms the polluting role of the smelting plant.     

沱江流域磷矿开采和加工过程中放射性环境问题探讨

大多数磷矿伴随着高含量的放射性元素U,通过对龙门山地区磷矿开采和加工过程中U,Th迁移的研究,初步查明了沱江流域放射性环境问题。研究结果显示,除含U磷块岩外,四川省磷肥及磷矿石中U含量水平相对偏高,磷矿开采加工是造成区域放射性元素含量偏高的主要原因;磷矿加工过程中放射性元素U,Th主要迁移到中间产物及最终产品中;磷石膏的堆放对周边土壤环境的放射性影响,水平方向上已超过2 km,垂向上近50 cm;磷矿的开采与加工已对流域产生了一定程度的放射性环境影响。     

抗旱肥料的诞生及其意义

实践证明，用磷铝质岩加工制成的新肥，不仅肥效显著，更有巨大的抗旱能力。据多年来的田间观测及初步研究成果可知，它的抗旱性能，主要由于共生的稀土中镧系所致。另在新肥生产中，要开展ＳＯ２的回收，并制得硫酸系列产品，提高厂家经济效益。化学肥料抗旱性能的发现，为其提供了极富前景的理论课题，并将产生明显的经济效益。     

磷矿的分布、特征与开发现状

世界磷矿储量近695亿t(2019年),但分布不均,磷矿储量最为丰富的北非地区集中了全球80％以上的磷矿资源.该区域的摩洛哥和西撒哈拉是世界磷矿资源最为丰富的国家,2019年其磷矿储量达500亿t,占世界的近72％.目前世界上主要利用的磷矿类型为沉积型磷块岩矿,其最主要的成矿时代为震旦—寒武纪和中生代—新生代,前者以中...     

微波消解-氢化物发生原子荧光光谱法同时测定化肥中的砷和汞

采用微波消解对样品进行前处理,建立了氢化物发生-双道原子荧光光谱同时测定化肥中砷和汞的方法。以20 g/L KBH4为还原剂,8%的盐酸为载液,测定砷和汞的负高压均为270 V,砷的灯电流为60 mA,汞的灯电流为20 mA。讨论了常见元素对测定的干扰,40 g/L的主量元素N、P、K,10倍于砷、汞浓度的杂质元素Te、Ca、Zn、Cu、Cr、Mn、Ni、Sb、Sn、Pb对砷和汞测定的影响满足分析要求。方法测定砷和汞的线性范围As为0.68～100μg/L,Hg为0.12～10μg/L;检出限As为0.68μg/L,Hg为0.12μg/L;方法精密度(RSD,n=5)低于8%。该方法具有前处理简便快速、易于操作、灵敏度高等特点,能满足化肥中砷和汞同时测定的要求。     

桂东南荔枝生长营养元素农业地球化学研究

桂东南是中国重要的荔枝产区,以梧州地区为例,重点对沙头和古凤两处荔枝种植园进行了生态地球化学调查,采集了荔枝园施肥圈内、外土壤,出露的代表性基岩,以及荔枝叶、青果和熟果样品,实测了大量和微量矿质元素、稀土元素,以及土壤营养元素有效态的含量。通过计算荔枝对土壤营养元素的吸收率及荔枝生长与结果期对营养元素的需求,查明本区荔枝生长的特征营养元素为Ca、K、Mg、Mn、P、Zn、Cu、B、Fe和REE。荔枝结果期的特需营养元素为P、Mg、Mo、Cu、Zn、Ko荔枝结果早和晚期特需元素分别为Ca、Si、B和Cu、Fe、K。在岩石-土壤-荔枝株生态循环系统中,本区营养元素在土壤中保持一定的积累,提供荔枝生长的需求,因此为荔枝宜种区;但全区土壤B缺乏,Zn、Mo局部不足。Ca、K、Zn在两区岩石土壤中分布不同,可能是造成沙头荔枝比古凤荔枝迟熟的主要农业地球化学因素。研究区有害元素Pb、Cd在土壤中积累是值得关注的土壤环境问题。     

Hydrochemistry, mineralogy and chemical fractionation of mine and processing wastes associated with porphyry copper mines: A case study from the Sarcheshmeh mine, SE Iran

The Sarcheshmeh is one of the largest Oligo-Miocene porphyry Cu deposits in the world. Comparative hydrochemical, mineralogical and chemical fractionation associated with mining efflorescence salts and processing wastes of this mine are discussed. Hydrochemical results showed that rock waste dumps, reject wastes and old impoundments of tailings are the main sources of acid mine drainage waters (AMD) that contain potentially toxic metals such as Cd, Co, Cu, Mn, Ni and Zn as well as Al. Episodic fluxes of highly contaminated acidic waters were produced in a tailings dam over a short period of time. Secondary soluble minerals provide important controls on the quality of AMD produced, especially in old, dry tailings impoundments. Secondary sulfate minerals such as gypsum, magnesiocopiapite, hydronium jarosite, kornelite and coquimbite were found in rock waste drainages and in old weathered reject wastes. Highly soluble secondary minerals such as gypsum, eriochalcite, and bonattite are also observed in an evaporative layer on old tailings impoundments. Chemical fractionation patterns of potentially toxic elements showed that the geochemical behavior of metals is primarily controlled by the mineralogical composition of waste samples. Elements such as Co, Cr, Cu, Mn, Ni and Zn are readily released into the water soluble fraction from efflorescence salts associated with rock waste drainages, as well as from the evaporative layer of old tailings. Potentially toxic elements, such as As, Mo and Pb, are principally adsorbed or co-precipitated with amorphous and crystalline Fe oxides, but they may also be associated with oxidizing, primary sulfides and residual fractions. Following the development of the dammed tailings pond, the secondary minerals were dissolved, producing acidic waters contaminated by Al (154 mg L⁻¹), Cu (150 mg L⁻¹), Cd (0.31 m gL⁻¹), Co (2.13 mg L⁻¹), Mn (73.7 mg L⁻¹), Ni (1.74 mg L⁻¹), Zn (20.3 mg L⁻¹) and Cl (1690 mg L⁻¹). Therefore, the potential use of recycled water from the Sarcheshmenh dammed tailings pond is diminished by the presence of corrosive ions like Cl⁻ in highly acidic fluids that promote corrosion of pipes and pumps in the water recycling system.     

Geochemistry of phosphate bearing sedimentary rocks in parts of Sonrai block,Lalitpur District,Uttar Pradesh,India

Major, trace and rare earth elements of phosphatic rocks around Sonrai block of Paleo-Mesoproterozoic age having phosphatic breccia, quartzite, shale, sandstone, limestone and ironstone, have been determined to evaluate their correlation, relationship with the phosphorus content, the nature of possible substitution of various elements and regional distribution pattern over the area. The study indicates that the number of elements is substituted in the apatite structures; few of them are associated with phosphate and carbonate minerals. The variable concentration of major, trace and rare earth elements in the phosphatic rocks has been influenced by various physico-chemical processes involved during weathering and leaching of the source rocks. The distribution of the major, trace and rare earth elements is controlled by the environmental variations in the sediment water interface. The majority of trace elements were mainly influenced by the principle adsorbents like the phosphate minerals in addition to clay, iron oxides and silicate minerals. The PAAS normalized REE patterns of Sonrai block of phosphorites are characterized by negative Ce anomalies and Positive Eu anomalies. It is inferred from the distribution and interrelationship of major, trace and rare earth elements that the deposition of phosphate minerals might have occurred in highly oxidizing to slightly reducing conditions in supratidal to intertidal continental margins and shallow marine environment. The deposition was controlled by marine upwelling leading to excess charge of phosphate in certain zones of phosphogenic basins, lithologic facies variations in restricted circulations of basinal waters and electrochemical factors such as negative Eh, pH and other factors, which influenced the deposition of phosphates. The replacement, precipitation in voids and fissures and diagenesis were also important mechanisms of phosphate generation in Sonrai basin. The main source for various elements may be the minerals of cratonic mass of Bundelkhand Granitic Complex, a basement of Bijawar Basin, which also provided land derived phosphorus through weathering of the terrestrial cover.     

Environmental geochemistry of Zarshuran Au-As deposit, NW Iran

Zarshuran deposit is the most famous and important As-Au mine in Iran. However, there is no information on the impact of mining activity on the surrounding environment, especially on water systems. This paper attempts to document the concentration of arsenic and associated elements in waters and sediments resulting from the mining history of Zarshuran, a period covering hundreds of years. Water and sediment samples collected from Zarshuran Stream indicate high content of some potentially toxic elements, especially of As which ranges from 0.028 to 40 ng/l in water and 182 to 36,000 mg/kg in sediment samples. Mining activity, exposure of a large volume of mining wastes to weathering, and the anomalously high background of trace metals in the mining area are considered to be the main sources of heavy metal pollution.     

Combination of single and sequential chemical extractions to study the mobility and host phases of potentially toxic elements in airborne particulate matter

Risk assessment of metals associated to airborne particulate matter (PM) has usually been based on the analysis of their total concentrations, which is a poor indicator of metal mobility. Chemical fractionation processes may provide an additional level of information, however, chemical complexity and small sample sizes do not allow to combine several extraction methods. Additionally, analysing the metal concentrations during the extractions exceptionally provides restricted information about metals’ speciation. To overcome these limitations we collected total suspended particulate matter (TSP) samples from the air filters placed in the air supply channel of methane-heated turbines of thermal power stations which allows collecting large amounts of TSP materials. Additionally, we combined single and sequential chemical extractions in which not only the concentrations of potentially toxic elements (PTE) (Cd, Cr, Cu, Ni, Pb, Zn) but also that of the major chemical components (Al, Ca, Fe, K, Mg, Mn, Na, P, S, Ti) were analysed. Our aims were to study these metals’ mobility and speciation through the study of their association to major chemical components.Accumulation of the studied PTEs in the TSP material suggests moderate contamination for Ni, Cd and Cr whereas a heavy one for Cu, Zn and Pb. Three groups of these PTEs could be distinguished based on their mobility. The highly mobile Zn and Cd (large ratios of water and weak acid soluble fractions) can be considered as especially harmful elements to environment. The moderately mobile Pb and Cu (large ratios of reducible and oxidizable fractions, respectively) may potentially have a negative effect on the environment, whereas the immobile Cr and Ni cannot be expected to pose a serious risk. Based on the statistical evaluation of extraction data, the potential phases for Zn and Cu are presented by metal-sulphates, -nitrates, -chlorides, -carbonates and -hydroxides, as well as sorbed forms. Lead primarily hosted by metal-carbonates and sorbed forms, as well as by -hydroxides, whereas Cu by organic matter. Finally, Cr and Ni are mostly incorporated into very resistant phases, most probably by magnetite or other resistant metal-oxides.Combination of single and sequential extractions, as well as that of the analysis of not only the target elements but also the major chemical components were found to be a very effective tool to study the host phases of PTEs in the TSP material. The necessity for relatively large sample amounts for such analyses could be fulfilled using special sampling methodology; however, obvious disadvantages of this kind of sampling must be taken into account when resulted data are evaluated.     

Soil geochemical signature of urbanization and industrialization – Chicago, Illinois, USA

The concentrations of 45 elements in ambient (not obviously disturbed) surface soils were determined for 57 sites distributed throughout the city of Chicago, Illinois in the upper Midwestern United States. These concentrations were compared to soils from 105 sites from a largely agricultural region within a 500-km radius surrounding the city and to soils collected from 90 sites across the state of Illinois. Although the bulk composition of the Chicago urban soils reflects largely natural sources, the soils are significantly enriched in many trace elements, apparently from anthropogenic sources. The median concentration of Pb in Chicago soils is 198 mg/kg, a 13-fold enrichment compared to regional concentrations. Zinc (median 235 mg/kg), Cu (59 mg/kg), and Ni (31 mg/kg) are also enriched from 2- to 4-fold in Chicago soils and all four elements show strong mutual correlations. These elevated concentrations are most likely related to vehicular and roadway sources and represent uneven distribution across the city as airborne material. Other airborne particulate material from a combination of fossil fuel combustion, waste incineration, and steel production may contribute to apparent elevated concentrations in Chicago soil of Fe (median 2.9%), Mo (5 mg/kg), V (82 mg/kg) and S (0.09%). Chicago soils are enriched from about 1.6- to 3-fold in these elements. Enrichments in P and Se may be caused by direct addition of phosphate fertilizer to parklands, lawns and gardens. The density of the sampling (1 site per 10 km²) is inadequate to define the distribution of the observed enrichments within the city or to predict soil compositions for most of the areas between sample sites, but does provide a statistically significant signature of the history of urban and industrial activity within the city in contrast to the surrounding agricultural lands.     

Trace elements in ferromanganese concretions,gibbsite spots,and the surrounding terra rossa overlying dolomite: Their mobilization,redistribution and fractionation

The mobilization, redistribution and fractionation of trace elements during chemical weathering processes have been investigated on a 4.05 m thick terra rossa profile overlying dolomite on the Yunnan-Guizhou Plateau, in Southwest China. In this in situ weathering profile, the ferromanganese concretions and the gibbsite spots coexist in the terra rossa saprolite. The mass-balance evaluation reveals that titanium, Nb and Hf in the terra rossa matrix are conservative elements during chemical weathering compared to Zr. The elements of Li, Sc, V, Cr, Fe, Ga, As, Mo, Cs, Ce, Ta, Tl, Pb and Th in the terra rossa matrix include additions from external sources. Beryllium, Mn, Co, Ni, Cu, Rb, Ba and La are depleted in the shallow parts of the terra rossa profile and enriched in the deep parts. The elements of Zn, Sr, Y, Cd, Sn and U in the terra rossa profile are lost during weathering. Compared to the terra rossa matrix, the ferromanganese concretions are significantly enriched in most trace elements, especially Mn, Co, Cd, Ce, Tl and Pb. In contrast, the gibbsite spots are depleted in all trace elements, except for U. The results regarding specific inter-element relationships indicate that most trace elements have different inter-element relationships in the ferromanganese concretions, the gibbsite spots and the terra rossa matrix. This suggests that the behavior of many trace elements during mobilization and redistribution differs from their behavior during incorporation into secondary mineral phases, especially the Mn and Fe oxides and/or oxyhydroxides in the ferromanganese concretions. It is worthy to note that the fractionation between Ce and Mn occurs under intensive chemical weathering conditions. Correspondingly, beryllium exhibits a similar geochemical behavior as that of rare earth elements (except for Ce) and Y during surface weathering.     

Uranium redistribution in weathered conglomerates of the early precambrian pongola supergroup, South Africa - inferences from a study by alpha spectrometry and fission track micromapping

Samples of potentially uranium-bearing conglomerates from deeply weathered outcrops of the 2900 to 3200 m.y. old Pongola Supergroup were investigated from three different localities in the southeastern Transvaal and northern Zululand. Uranium isotope and uranium fission track analyses were carried out to study and to unravel the complex uranium redistribution processes which took place and which are still in progress in the weathering zone of the conglomerates. It is proposed that the combination of the two radiochemical methods can provide valuable information assisting the exploration of uranium mineralization in early Precambrian quartz-pebble conglomerates.     

Potential environmental impact at São Domingos mining district (Iberian Pyrite Belt,SW Iberian Peninsula): evidence from a chemical and mineralogical characterization

São Domingos like other long-term activity mines of the Iberian Pyrite Belt (IPB) dating back to pre-Roman times, is supposed to produce considerable amounts of mining wastes which cause significant downstream negative environment impact related to the acid mine drainage (AMD) production and high content of potentially toxic metals and metalloids in Chanza and Guadiana Rivers. The AMD production of a given mining waste depends on the ratio of its acid production to neutralizing phases. In this work, a chemical and mineralogical characterization of the sulphide-rich wastes from São Domingos has been developed to discriminate which residues are the main sources of AMD generation. A total of 47 representative samples of the different residue types were collected to estimate their possible contamination hazards through detailed studies of (1) for a mineralogical characterization: reflected-light optical microscope, scanning electron microscope (SEM) and XRD analysis; and (2) for a chemical characterization: bulk-rock analysis. AMD prediction by the standard acid-base accounting method (ABA) was used in order to determine the acidification potential of each residue type. This study also offers an estimation of the contribution of toxic elements to the environment, being thus, a base for future remediation actions at São Domingos and other abandoned massive sulphide mines within the IPB.     

Effects of forest slash and burn on the distribution of trace elements in floodplain sediments and mountain soils of the Subandean Amazon,Peru

Forest clearing through slash and burn to open up agricultural land is an ongoing process in large parts of the Amazon Basin. This activity severely affects the structure and balance of the natural ecosystem, and also has the potential to cause substantial changes in landscape geochemistry. The latter is the topic of this study, with special attention on translocation of potentially toxic trace elements from deforested areas to downstream aquatic and terrestrial systems. Sampling of floodplain sediments and mountain soils (Inceptisols on redbed lithologies) was carried out in two adjacent Subandean river basins, with deforestation extents of ca. 1/3 and 2/3 of the basin areas. Several toxic and potentially toxic metals (e.g., Hg, Cd, Pb, Cu and Ni) and other major and minor elements showed concentration peaks at certain depths in the alluvial deposits of both basins. These peaks were associated with organic matter, and occurred just below layers of combustion residues originating from burning of in situ biomass. Downward migration of particles originating in the combustion residues is suggested to be the direct mechanisms of the metal enrichments. Further evidence of an in situ origin of the metal peaks in the sediments was provided by the geochemical composition of soils located upstream of the floodplains. Disturbed soils (i.e. soils of pasture, coffee plantations, secondary forest and recently swidden fields) were found to be similar to soils under natural forest. Moreover, trace element concentrations in floodplain deposits were similar in the two drainage basins despite the large difference in exploitation degree. Thus, no evidence was found of large scale (basin-wide) increases in trace-metal leaching or translocation as a result of the extensive deforestation and agricultural land-use that has been practiced in the Amazonian highland jungle over more than 100 a.