Catchment and in-stream influences on metal concentration and ochre deposit density in upland streams, Northern Ireland

Metal concentrations from stream waters in two geological blocks in Northern Ireland were compared to determine the contributions of catchment characteristics and in-stream conditions. One block is composed of metamorphosed schist and unconsolidated glacial drift with peat or peaty podzol (mainly humic) soils, while the other block consists of tertiary basalt with brown earth and gley soils. Water samples were collected from 52 stream sites and analysed for iron (Fe), manganese (Mn) and aluminium (Al) as well as a range of other chemical determinands known to affect metal solubility. Densities of metal-rich ochre deposit were determined for stream bed stone samples. Higher conductivities and concentrations of bicarbonate, alkalinity, calcium and magnesium occurred on basalt than on schist. Despite higher Fe and Mn oxide concentrations in basalt-derived non-humic soils, stream water concentrations were much lower and ochre deposit densities only one-third of those on schist overlain by humic soils. Neither rock nor soil type predicted Al concentrations, but pH and dissolved oxygen did. Peat-generated acidity and the limited acid neutralising capacity of base-poor metamorphosed schist have resulted in elevated concentrations of metals and ochre deposit in surface waters.     

Base-metal-rich metamorphosed black shales associated with Proterozoic ophiolites in the Kainuu schist belt,Finland: a genetic link with the Outokumpu rock assemblage

Metamorphosed black shale is an essential component of the Early Proterozoic Outokumpu rock assemblage, together with serpentinite, calc-silicate rock and quartz rock. This rock assemblage, hosting the major Cu-Co-Zn deposits of Outokumpu and considered ophiolitic in origin, has also been encountered to the northwest in the Kainuu schist belt. The rift basin encompassing the two areas was intruded by ophiolite complexes 1.96–1.97 billion years ago. Remnants of ultramafites are met as serpentinite and talc-carbonate rock lenses bounded by faults along the western margin of the Kainuu schist belt. The black schist formations range in thickness from tens of metres to 400 m. Metal-rich layers occur close to the serpentinite bodies. The most extensive formations of metal-rich black schist (300 Mt, 0.26% Ni, 0.14% Cu, 0.53% Zn) have been encountered at Talvivaara. The lithological, mineralogical and geochemical results indicate a genetic link between the Jormua, Talvivaara, Alanen and Pappilanmäki prospects in the Kainuu schist belt and the Outokumpu rock assemblage.     

Effect of low-molecular-weight organic acids on the distribution of mobilized Al between soil solution and solid phase

Low-molecular-weight (LMW) organic acids occur widely in soils. Results in pure mineral systems and podzols suggest that LMW organic acids can promote the dissolution of Al from kaolinite, Al oxides and soils, but limited information is available concerning the role of these organic acids on Al mobilization in variable charge soils as yet. This paper deals with the effect of LMW organic acids on Al mobilization and mobilized Al distributed between the solution phase and exchangeable sites in two acidic variable charge soils. The results indicated that LMW organic acids accelerated Al mobilization through proton- and ligand- promoted reactions. The ability of different organic acids to mobilize Al followed the order: citric acid > oxalic acid > malonic acid > malic acid > tartaric acid > salicylic acid > lactic acid > maleic acid. This order was in general agreement with the magnitude of the stability constants of Al–organic acid complexes. The ratio of soluble Al to exchangeable Al also increased as the stability constants increased. These results showed that the organic acids with strong Al-complexation capacity were most effective in Al mobilization, whereas the weak organic acids promoted the retention of mobilized Al by the soil exchangeable sites. Increase in both organic acid concentration and solution pH promoted Al mobilization and also increased the ratio of soluble Al to exchangeable Al due to the increase in the concentration of the effective organic ligands, especially in the strong organic acid systems. These findings may have their practical significance for establishing more effective amelioration procedures for variable charge soils with increased acidity and higher mobility of Al.     

Biogeochemical weathering of serpentinites: An examination of incipient dissolution affecting serpentine soil formation

Serpentinite rocks, high in Mg and trace elements including Ni, Cr, Cd, Co, Cu, and Mn and low in nutrients such as Ca, K, and P, form serpentine soils with similar chemical properties resulting in chemically extreme environments for the biota that grow upon them. The impact of parent material on soil characteristics is most important in young soils, and therefore the incipient weathering of serpentinite rock likely has a strong effect on the development of serpentine soils and ecosystems. Additionally, porosity generation is a crucial process in converting rock into a soil that can support vegetation. Here, the important factors affecting the incipient weathering of serpentinite rock are examined at two sites in the Klamath Mountains, California. Serpentinite-derived soils and serpentinite rock cores were collected in depth profiles from each sampling location. Mineral dissolution in weathered serpentinite samples, determined by scanning electron microscopy, energy dispersive spectrometry, electron microprobe analyses, and synchrotron microXRD, is consistent with the order, from most weathered to least weathered: Fe-rich pyroxene > antigorite > Mg-rich lizardite > Al-rich lizardite. These results suggest that the initial porosity formation within serpentinite rock, impacting the formation of serpentine soil on which vegetation can exist, is strongly affected both by the presence of non-serpentine primary minerals as well as the composition of the serpentine minerals. In particular, the presence of ferrous Fe appears to contribute to greater dissolution, whereas the presence of Al within the parent rock appears to contribute to greater stability. Iron-oxidizing bacteria present at the soil–rock interface have been shown in previous studies to contribute to the transition from rock to soil, and soils and rock cores in this study were therefore tested for iron-oxidizing bacteria. The detection of biological iron oxidation in this study indicates that the early alteration of these Fe-rich minerals may be mediated by iron-oxidizing bacteria. These findings help provide insight into the incipient processes affecting serpentinite rock weathering, important to the development of extreme serpentine soils and the biota that grow on them.     

酸性条件下红壤中铝的活化及环境意义

利用动态反复浸提模拟实验研究了4种红壤中固相铝的活化过程。结果表明，红壤酸化程度与土壤表面变换性铝呈正相关关系。当高强度外源H^ 输入土壤后，有机铝和无机铝均可活化。浸提初期以弱键合的有机铝活化为主，当浸提到一定程度时，弱键合有机铝亏损，无机铝活化的相对重要性显示出来。20次浸提后，宁海红壤，嵊县红壤及永春红壤的铝总活化量中无机铝占主要部分。当土壤酸化到一定程度时（如屯溪红壤）有机铝和无机铝均亏损，铝的活化量很低。酸性条件下弱键合有机铝的快速活化产生高浓度的可溶性铝以及随后的快速亏损都将对生态环境产生重要影响。     

pH-dependent copper release in acid soils treated with crushed mussel shell

The aim of this study was to assess the influence of pH on copper mobilization in two copper-rich acid soils (from vineyard and mine) amended with crushed mussel shell. Crushed mussel shell amended soils (0–48 Mg ha^?1) were subjected to the effect of several acid and alkali solutions in a batch experiment in order to study their copper release. Copper distribution was studied in decanted soils from batch experiments using a sequential extraction procedure, whereas the effect of crushed mussel shell on copper release kinetics was studied using a stirred flow reactor. When soils were treated with acid solutions, the copper mobilization from non-amended soils was significantly higher than from the amended samples. Major changes in copper fractionation were an increase of the acid soluble fraction in acid-treated vineyard soil samples with shell dose. For the mine soil, the oxidable fraction showed a relevant diminution in acid-treated samples at the highest crushed mussel shell dose. For both soils, copper desorption rates diminished up to 86 % at pH 3 when crushed mussel shell was added. At pH 5, copper release rate was very slow for both soils decreasing up to 98 % for the mine soil amended with the highest shell dose, whereas no differences were observed at pH 7 between amended and non-amended soils. Thus, crushed mussel shell addition could contribute to reduce potential hazard of copper-enriched soils under acidification events.     

Pillow structures in serpentinite,Tagadur, Nuggehalli schist belt,Karnataka

Pillow structures developed in serpentinite is described from the Nuggehalli schist belt, Karnataka. Chemistry of the rock reveals that the serpentinite is a direct representation of mantle material.     

The potential use of serpentinite in the passive treatment of acid mine drainage: batch experiments

The efficiency of serpentinite as an alternative alkalinity generating material for the passive treatment of acid mine drainage (AMD) was assessed in the laboratory. Three series of batch experiments were designed for the passive treatment of a low pH (1.6) AMD synthetic solution containing 2,500 ppm Fe²⁺, 6,600 ppm SO₄^2–, 10.5 ppm Al, 15 ppm Ni, and traces of Cr, Mn and Cu. The influencing factors studied were: the effect of water/rock ratio, residence time, type of the alkalinity generating material (dolomite, magnesite, marble, serpentinite), and nature of the system (open vs. closed cells). The variations in solution chemistry observed in the open cells indicate that a lower water/rock ratio (0.33 ml/g) was the most efficient for metals removal. The optimal residence time in open cells was 24 h to reach the higher pH values. In the closed cells laboratory setup, synthetic AMD was placed in contact with the various alkaline materials for three different contact times (24, 48, 72 h). The optimal pH was reached after 48 h and did not change appreciably for longer contact time, and the best results for metal removals were obtained with marble and serpentinite. Single treatment efficiency was compared with a successive treatment approach. The most promising results were obtained with a five step treatment: (1) pre-treatment in a closed cell using serpentinite, (2) aeration and settling, (3) treatment in an open cell using marble, (4) final aeration and settling, and (5) filtration with a coarse silica sand. With this configuration, the final pH was 6.5 and pronounced metals depletion was achieved (100% for Al, 99.95% for Fe, 85.7% for Ni).     

The bioavailability of Al in soils to tea plants

In order to understand the relationship between forms of Al in soils and the uptake of Al from soil into tea plants, tea leaves and soils were collected from 13 tea gardens in the east of China. The Al concentration measured in the tea leaves was found to be best predicted by ‘available’ Al extracted by 0.02 M CaCl₂. The relationship appears to be linear, with a correlation coefficient of 0.77 (P=0.01). The Al content of tea leaves increases with a decrease of soil pH. This relationship is non-linear with a marked increase in leaf Al for soils with pH <5.0. The amounts of Al in soils extracted with 0.02 M CaCl₂ was much less than other forms of Al in soils. The amount of Al measured in the tea leaves was directly related to both the ‘available’ form of Al in the soils and soil pH. Soil pH was identified as a major factor that controls the uptake of Al from soil into the tea leaves.     

浙江临安东部地区土壤硒分布特征及影响因素

对浙江临安东部地区表层土壤进行地质调查,发现了大面积富硒土壤,并总结了表层土壤硒的分布特征及影响因素。研究区表层土壤硒含量平均值为0.38×10-6;不同土壤类型硒含量差异较大,其中黄壤硒含量最高,平均值为0.58×10-6。概率累积曲线表明,土壤硒主要来源于自然背景,受外源输入组分影响较小。土壤硒含量与V、Mo、Ni、Cr含量呈显著正相关,与有机质关系密切,与pH值相关性较好。荷塘组碳质页岩、硅质岩和宁国组碳质页岩是该区富硒土壤的主要来源。     

福建铁观音茶园生态地球化学特征

东南沿海是铅等重金属的地球化学高背景区。该地区广泛分布酸性红壤,酸雨沉降、不适当施肥导致土壤酸化以及由此引发土壤重金属生态风险令人关注。以福建省铁观音主产区为研究区,采集了79个茶园的表层和亚表层土壤样、茶叶样品,测定了重金属元素以及土壤常量元素和理化指标。研究表明,福建铁观音茶园土壤中Hg、Pb、Se、Zn高含量主要由地质背景所引起,土壤常量组分、有机质、酸碱度等理化条件对土壤元素含量有一定的影响;铁观音茶树老叶中As、Cd、Cr、Hg、Se、Pb、F等非植物营养元素含量明显高于嫩叶,显示这些元素随植物生长逐渐累积的特征,而嫩叶中植物生长必需的营养元素Cu、(Ni)、Zn则高于老叶,反映出微量营养元素在茶叶生长部位相对富集的特征;多数情况下土壤与茶叶间元素含量相关性差,说明茶树对土壤元素的吸收累积受到多种复杂因素的影响。研究表明茶叶与土壤Pb、Cr具有显著正相关性,为建立铅污染土壤生态效应预测评价模型提供了基础依据。     

Citrate sorption and biodegradation in acid soils with implications for aluminum rhizotoxicity

Citrate and other organic acids play an important role in the rhizosphere and pedogenic processes. Although secreting citrate from roots in response to Al and heavy metal stress has been recognized as a central mechanism for plants to avoid toxicity, the efficiency of root citrate on metal detoxification is still contradictory in acid soil with abundant oxide minerals that serve as a potential sorption site for citrate. The objective of this study was to investigate sorption and biodegradation of citrate in subtropical acid soils with different mineralogical properties. A batch experiment was conducted to assess the possible fates (adsorption and biodegradation) of citrate in the three acid soils (Cecil, Creedmoor and Norfolk) under microbial-active and inactive conditions. Citrate adsorption isotherms for all soils were adequately described by the Freundlich equation with the R² value being over 0.90. The Cecil soil had the highest affinity for citrate adsorption among the soils with 99% adsorption observed throughout the citrate concentration range, which was due primarily to the abundant Al and Fe oxides. Citrate sorption to the mineral phase significantly reduced its biodegradation by 56%, 65% and 99% for the Creedmoor, Norfolk and Cecil soils, respectively. The results suggest the efficiency of rhizosphere processes for Al detoxification by root-secreted citrate would be significantly reduced in acid soil with abundant Al and Fe oxides.     

土壤有毒元素镉污染修复方法探讨

植物中的镉含量与土壤溶液中的镉含量成正相关关系，与土壤的pH值成负相关关系，土壤的酸碱度对植物吸收重金属元素具有显著的控制作用。因此，通过提高呈酸性土壤的pH值可以降低植物中的镉含量，解决植物中的镉超标问题。在土壤中施用硅酸钙、碳酸钙、熟石灰、硅酸镁钙等农用石灰性物质，特别是熟石灰，是提高土壤pH值最有效、最经济、最可行的方法。利用我省丰富而廉价的粘土资源，配合施加碱性物质，可更进一步提高土壤“抵抗力”，确保重金属镉超标区植物的安全。     

母岩类型对土壤和沉积物镉背景的控制: 以贵州为例

镉是土壤和沉积物中最受关注的重金属污染物之一,合理确定其自然背景对于环境管理具有重要意义。然而,由于不同基岩中该元素含量差异很大,且在风化成壤过程中元素也可能发生富集或贫化,造成该元素具有很大的空间变异,甚至可以超出筛选值和管制值。本文从基岩-土壤地球化学元素迁移规律出发,以基岩类型较复杂、镉空间变异较大的贵州省为例,基于土壤和沉积物调查数据,建立基岩与土壤或沉积物中镉含量的对应关系,筛选合理的岩性类型端员和背景区域划分方法,为环境管理确定基础背景。研究结果显示,岩性类型是造成土壤镉空间变异的重要因素,石灰岩(排除白云岩)、玄武岩、辉绿岩和碳质页岩等是造成土壤高镉背景的重要岩石类型。相对母岩类型,岩石所在地层时代对土壤镉背景的影响不太明显。本文通过大量数据统计,给出了相对较纯的岩性发育土壤的镉背景值和变异区间,不纯岩性或地质单元发育土壤的镉背景值可能受多个岩性端员的影响。     

Mobilization of aluminium and magnesium by roots of banana (Musa spp.) from kaolinite and smectite clay minerals

Banana plants (Musa spp.) are very sensitive to Al, which is mobilized in acid soil conditions. These plants may, however, contribute to their own intoxication because their roots can excrete protons in large quantities. The authors studied the mobilization of Al by banana roots from clay minerals in experimental designs exacerbating the root–mineral contact. The plants were grown on agarose-gel or sand substrates previously mixed with smectite (montmorillonite) and kaolinite as sole source of Al. The pH and the ion concentrations in the aqueous and exchangeable phases of the substrates were determined as concentrations of Al, Ca, Mg and K in plants. In both agarose and sand substrates, pH significantly decreased in the close vicinity of roots, relative to the bulk substrate. This root-induced acidification involved a preferential mobilization of Al in kaolinite substrates and of Mg in smectite substrates, and thereby a significant plant uptake of Al and Mg from these respective substrates. Root-induced weathering of kaolinite and montmorillonite thus suggests that the mobilization of, respectively, Al and Mg are the limiting steps in the dissolution of these respective minerals, just as demonstrated in previous chemical weathering studies.     

Experimental investigation on aluminum release from haplic acrisols in southeastern China

A sequential dissolution technique and a prolonged extraction method were used to investigate aluminium (Al) release from 4 Haplic Acrisols in southeastern China. The results show that the order of acidification of the 4 soils is: Tunxi soil>Yongchun soil>Shengxian soil>Ninghai soil. The amount of exchangeable Al is directly proportional to the extent of soil acidification. Al was released from both organically bound and inorganic Al pools after acid input. During several initial cycles of extraction the release of Al was mainly from the weakly organically bound Al pool. After prolonged extraction, Al release from the inorganic Al pool became more important to the total dissolved Al due to a rapid depletion of the weakly organically bound Al pool. The sizes of readily reactive Al pools in the Ninghai soil and Shengxian soil are larger than in the Yongchun soil and Tunxi soil. Al released from the inorganic Al pool in the Ninghai soil, Shengxian soil and Yongchun soil after 20 cycles of extraction was higher than from the organically bound Al pool, whereas the opposite was the case for the Tunxi soil. A low saturation of Al binding on soil organic matter (SOM) does not necessarily lead to a low Al release as in the case of the Shengxian soil. Also a relatively high saturation does not necessarily ensure a large Al release from the Al pool as in the case of the Tunxi soil and Yongchun soil. Once both organically bound and inorganic Al pools are depleted of readily reactive Al phases due to high soil acidification, Al dissolution would be small even under strong acid input. The high concentration of aqueous Al after rapid Al release from the weakly organically bound Al pool and subsequent depletion of the pool may have significant ecological and environmental effects.     

Metal dispersion in groundwater in an area with natural and processed black shale – Nationwide perspective and comparison with acid sulfate soils

Black shale is often rich in sulfides and trace elements, and is thus a potential environmental threat in a manner similar to acid sulfate soils and active or abandoned sulfide mines. This study aims at characterising how exposed and processed (mined and burnt) black shale (alum shale) in Degerhamn, SE Sweden, affects the chemistry (Al, As, Ba, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Si, Na, Sr, S, U, V and Zn) of the groundwater. There were large variations in groundwater chemistry between nearby sampling points, while the temporal variations generally were small. Acidic groundwater (around pH 4), found in deposits of burnt and carbonate-poor shale where the conditions for sulfide oxidation were favourable, was strongly elevated in Al, U and several chalcophilic metals (Cd, Co, Cu, Ni and Zn). Cadmium and U were also, together with Mo, abundant in many of the near-neutral waters, both in the non-mined black shale bedrock and in the deposits of burnt shale. An extrapolation to a national level suggests that the dispersion of Ni from naturally occurring black shale is similar to that from anthropogenic point sources, while for Cd and As it is assessed to be approximately one tenth of that from point sources. The processed shale was, however, a much larger source of metals than the black shale bedrock itself, showing this material’s potential as a massive supplier of metals to the aquatic environment. A comparison of waters in contact with the processed Cambrian–Ordovician black shale in Degerhamn and acid sulfate soils of the region shows that these two sulfide-bearing materials, in many respects very different, delivers basically the same suite of trace elements to the aquatic environment. This has implications for environmental planning and protection in areas where these types of materials exist.     

粤北大宝山矿酸性排水中铅元素环境地球化学

粤北大宝山铁多金属矿床的开发给环境带来了严重的危害。采选冶产生的酸性排水及固体废弃物堆积的淋滤酸水,携带浸滤出的大量重金属离子流入下游河道,严重影响矿区及酸水流域的生态环境。结果表明,河流水中高Pb含量直接源于尾砂,并受水体pH值的显著影响。河流底泥能够大量聚集水体中的Pb,在水体pH值降低时,相对稳定存在的Pb会被再次从河流底泥中释放出来,形成河流二次污染。土壤中Pb含量受土壤pH值和土壤粒度的影响,食用蔬菜中Pb的高含量由土壤Pb高含量决定,并受土壤pH值的影响,通过改善农业灌溉水质,提高土壤pH值,可以降低蔬菜重金属Pb含量。     

广东省普宁市土壤硒的分布特征及影响因素研究

开展了广东省普宁市区域土壤硒调查研究,采集了413个表层土壤样品(0～20 cm)和103个深层土壤样品(> 150 cm),测定了土壤全硒含量,据此研究土壤硒分布特征及其影响因素。结果表明,普宁市土壤全硒含量变化于0. 16～2. 01 mg/kg,平均值为0. 63 mg/kg,总体上处于中硒及高硒水平,不存在缺硒和硒过剩土壤。砂页岩风化形成的赤红壤全硒含量较高,平均值达0. 86 mg/kg,以侏罗系页岩母质发育的土壤全硒含量最高,平均值达0. 89 mg/kg;三角洲第四系沉积物发育形成的水稻土全硒含量最低,平均值为0. 41 mg/kg。回归分析表明,土壤全硒含量与铁铝含量、有机碳含量具有极显著正相关,与p H呈极显著负相关。影响普宁市土壤硒含量的主要因素是成土母质,土壤p H、有机碳和铁铝含量及土地利用方式对土壤全硒含量分布与富集也有一定的影响。     

Early Cretaceous subduction of continental crust at the Diego de Almagro archipelago, southern Chile

In the Diego de Almagro archipelago of southern Chile, a quartz rich mica schist and a mylonitized granite contain Late Jurassic zircons of ca 166 and 170 Ma respectively. These rocks were metamorphosed during the Cretaceous in a subduction zone environment, which developed blueschist assemblages in metabasalts interleaved with the mica schist. The dated rocks were probably part of the acid large igneous province developed in southwestern Gondwanaland during the extensional phase which preceded the dismembering of the supercontinent. They constitute evidence that tectonic erosion of the margin occurred, as these siliceous igneous rocks, formed in the South American upper plate, were transported in the subduction zone to some 20 km depth prior to their exhumation. These rocks are in tectonic contact through the Seno Arcabuz shear zone, with late Permian turbidites of the Duque de York complex, which did not undergo blueschist metamorphism.