不同初始Fe(Ⅱ)浓度对施威特曼石生物合成的影响

施威特曼石(schwertmannite)已被证实是一种具特异性能的重(类)金属吸附新材料,生物方法合成的施威特曼石由于具备较好的表面吸附性能而受到更多关注。本文通过接种有嗜酸性氧化亚铁硫杆菌(Acidithiobacillusferrooxidans)的FeSO4-H2O矿物合成体系,研究了不同初始Fe2+浓度对Fe生物转化成施威特曼石效率的影响。结果表明,在Fe(Ⅱ)浓度(FeSO4.7H2O配制)设计为20、40、80和160 mmol/L,接种A.ferrooxidans菌密度达到6.0×107个/mL时,本实验条件下矿物重量y(g)与初始Fe2+浓度x(mmol/L)的关系为y(g)=0.036 67+0.008 520x-8.602.10-6x2;溶液TFe沉淀率y(%)与初始Fe2+浓度x(mmol/L)的关系为y(%)=39.68-0.221 0x+6.653.10-4x2。反应后期溶液中大量残留Fe3+在满足饱和指数SI>0的条件下不能析出矿物沉淀,进一步分析表明,Fe3+水解形成施威特曼石的可能机制是利用了Acidithiobacillus ferrooxidans菌氧化Fe2+释放的能量才得以实现,当Fe2+完全氧化不再供应能量时,Fe生物转化成施威特曼石的反应也达到了最大限度。     

利用尾矿砂制备镁铁氢氧化物实验研究

以金川铜镍矿尾矿酸浸液为原料,根据矿物沉淀pH值区间的不同,分步分离Fe、Mg的沉淀物以及有价金属Al、Co、Ni、Cu的混合沉淀物,进而制备具有高附加值的Fe(OH)3和Mg(OH)2,同时富集Co、Ni、Cu等有价金属。结果表明,当溶液pH值为3.8时可沉淀分离出主要成分为施威特曼石(schwertmannite)的氢氧化铁前驱体,pH值达到9.8时沉淀富集出Al、Co、Ni、Cu的混合氢氧化物,随即得到只含有Mg离子的溶液。在60℃条件下,将施威特曼石在pH值为12的NaOH溶液中老化36h,可以得到Fe(OH)3。同时,以NaOH调节只含有Mg离子的溶液至pH值为12.4时可获得Mg(OH)2。本研究为金属矿山尾矿的资源化综合利用提供了新的思路与方法。     

合成施威特曼石吸附Cu^2＋和Pb^2＋的实验研究

施威特曼石普遍存在于含大量SO42-的酸矿水中,其表面吸附的SO42-使得该矿物具有强吸附重金属离子的能力,可用于处理重金属离子污染。实验通过在不同浓度Cu2＋溶液中合成施威特曼石时发现,Cu2＋与施威特曼石的共沉淀量较低,FTIR分析表明Cu2＋与施威特曼石的羟基发生反应。开展施威特曼石吸附Pb2＋的实验,结果表明施威特曼石对Pb2＋的吸附符合Langmuir模型,施威特曼石吸附Cu2＋和Pb2＋后出现1545.4 cm-1和1435.0 cm-1（Cu2＋）两个吸收峰,可能是施威特曼石孔道表面形成了三元配合物。在241×10-6的初始浓度（与尾矿孔隙水的Pb2＋含量相近）下有61.4%的Pb2＋去除率,显示了较好的环境修复价值。     

广东大宝山铁龙AMD中赭色沉积物的含铁次生矿物研究

以广东大宝山铁龙酸性矿山废水(AMD)为研究对象,采集了7个采样点的赭色沉积物样品。利用X射线荧光光谱(XRF)、傅里叶变换红外光谱(FTIR)、X射线粉晶衍射(XRD)和场发射扫描电镜/能谱分析(FESEM/EDS),对AMD中赭色沉积物的矿物相及形貌进行鉴定。现场测定采样点水体物理化学参数(pH/Eh),探讨不同物理化学条件对含铁次生矿物相的影响。结果表明,大宝山铁龙AMD中赭色沉积物的含铁次生矿物主要有施威特曼石、黄钾铁矾、针铁矿、水铁矿等,此外沉积物中还含有七水铁矾、叶绿矾、四水白铁矾、针绿矾、纤铁矾、锡铁山石及羟铝矾等可溶性硫酸盐。施威特曼石具有带骨针棒状、海胆状形貌,针铁矿常呈针状及肾状集合体产出,黄钾铁矾呈六方板状,施威特曼石常可与黄钾铁矾或者针铁矿共生。赭色含铁次生矿物能在AMD较大范围的pH条件下存在,但倾向于Eh高的环境。当pH值增大时,施威特曼石有转变为针铁矿的趋势,并且针铁矿能保存施威特曼石的形貌特征。     

粤北大宝山酸性矿山废水中梯田状沉积物的次生矿物研究

粤北大宝山酸性矿山废水(AMD)中形成了呈独特梯田状构造的沉积物,其中的次生矿物可以吸持AMD中的重金属离子,对减少矿山环境的重金属污染有重要意义。本文采集了大宝山AMD中呈梯田状构造中的沉积物,利用多种手段分析了其主要矿物组成以及主要次生矿物的表面形貌特征,探究梯田状沉积物的成因。结果表明,梯田状沉积物的次生矿物以针铁矿、施威特曼石、黄钾铁矾为主,含少量石膏、斜方钙沸石等。针铁矿呈针状、球刺状集合体;施威特曼石呈海胆状、鳞片状,粒度为微米级,海胆状施威特曼石与球刺状针铁矿共生;黄钾铁矾呈不规则的球粒状、片状,与施威特曼石共生。研究表明微生物作用可能是形成铁质梯田状构造的关键因素。     

Cl-/SO42-铁盐对含可溶性胞外多聚物Acidithiobacillus ferrooxidans溶液中铁矿物形成的影响

铁细菌胞外多聚物作用下聚集的铁可通过氧化或者沉淀作用使铁稳定或沉积,从而形成铁矿物。本文基于铁细菌胞外多聚物(extracellular polymeric substances,EPS)对铁矿物形成的调控作用,介绍了Cl-/SO_4~(2-)的Fe(Ⅲ)或Fe(Ⅱ)盐作用下,含可溶性EPS的氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)溶液中铁矿物的形成,观察了溶液pH值变化及形成铁矿物的矿相与结构,并采用XRD、FTIR和FESEM对其进行表征。结果发现反应溶液中OH-离子可与Fe3+形成微米级"针垫"聚集球状或纳米级小球形施威特曼石和微米级"菱形"块状黄钾铁矾铁矿物沉淀。反应溶液中的可溶性EPS可调控和促进铁矿物的形成,但对Fe2+的氧化未产生影响;外源Fe盐可促进施威特曼石向黄钾铁矾转化。随着Cl-/SO_4~(2-)摩尔比例的增加(即Cl-含量的不断增加),两矿相间的转化明显受到抑制,且铁矿物颗粒之间的集聚作用明显减弱;反之,SO_4~(2-)含量升高时,有利于铁矿物间的转化和聚集球状颗粒形貌结构的形成。     

极端酸性环境下形成的施威特曼石（schwertmannite）及其环境学意义

施威特曼石(schwertmannite)是近年来发现存在于含SO42-丰富的极端酸性环境下的一种次生羟基硫酸高铁矿物,其结晶度较差,形态特殊,表面基团活性强,对其存在环境中有毒重(类)金属元素的迁移与钝化有重要影响。本文详细地介绍了施威特曼石的形成、组成结构、稳定性能、溶解度及其与重(类)金属元素的相互作用等方面的研究进展,并对其在地下水除砷中的应用前景进行了讨论。     

A.ferrooxidans培养过程中Al/Fe(摩尔比)对铁矿物形成产物的影响

主要研究了磷酸铝(Al PO4)的加入量对氧化亚铁硫杆菌HX3培养液中铁矿物形成的影响,并对相应沉淀产物进行了结构表征分析。结果表明,Al PO4的加入对细菌培养过程中Fe2+的氧化无明显影响,但可促进Fe3+的水解和初始铁矿物相的形成,也可加速黄钾铁矾的转化形成。Al/Fe(摩尔比)为0. 04～1的培养液中主要形成产物为施威特曼石和黄钾铁矾; Al/Fe为0. 4和1时另有磷酸铁矿形成。较高的Al/Fe比值和磷酸根含量有利于磷酸铁矿的形成。     

几种氢氧化铁对亚砷酸根的吸附及预处理方法的影响

笔者研究了3种铁氧化物(氢氧化物)对亚砷酸根阴离子的吸附作用。三种吸附剂分别是Fe(OH)3凝胶,其真空微波干燥和80℃常规干燥产物。实验结果表明,将氢氧化铁凝胶与亚砷酸钠溶液混合后,六分钟内溶液的pH值从9.71升高至10.36,说明亚砷酸根取代了氢氧化铁中的氢氧根。反应40分钟后,pH值下降,原因很可能是被吸附的亚砷酸根表面络合体从单齿络合转变成为单核—双齿络合体并释放质子。pH值降低并不意味着吸附作用的结束,而是表明了反应类型的转变。温度和溶解空气对这两种反应的影响很小。将吸附剂超声波处理后,亚砷酸根的吸附总量增加了,不过…     

镁铝铟类水滑石的合成与表征

采用共沉淀法合成了含有金属铟离子的碳酸根型水滑石，研究了沉淀方式、温度、pH值、老化时间和镁铝铟摩尔比这些对镁铝铟类水滑石（Mg-Al-In HTlc)的纯度和结晶度有影响的合成条件。通过XRD及IR表征，结果表明以恒定pH值的高过饱和沉淀法，控制其沉淀和老化温度在65℃、洗涤温度为室温，pH值为10－11.5，老化时间为8h,n(In^3 )/n(M^3 )在0.1-0.8之间可以得到纯度高和结晶好的镁铝铟类水滑石。     

Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands

We examined the transformations of Fe and S associated with schwertmannite (Fe₈O₈(OH)₆SO₄) reduction in acidified coastal lowlands. This was achieved by conducting a 91 day diffusive-flux column experiment, which involved waterlogging of natural schwertmannite- and organic-rich soil material. This experiment was complemented by short-term batch experiments utilizing synthetic schwertmannite. Waterlogging readily induced bacterial reduction of schwertmannite-derived Fe(III), producing abundant pore-water Fe^II, SO₄ and alkalinity. Production of alkalinity increased pH from pH 3.4 to pH ∼6.5 within the initial 14 days, facilitating the precipitation of siderite (FeCO₃). Interactions between schwertmannite and Fe^II at pH ∼6.5 were found, for the first time, to catalyse the transformation of schwertmannite to goethite (αFeOOH). Thermodynamic calculations indicate that this Fe^II-catalysed transformation shifted the biogeochemical regime from an initial dominance of Fe(III)-reduction to a subsequent co-occurrence of both Fe(III)- and SO₄-reduction. This lead firstly to the formation of elemental S via H₂S oxidation by goethite, and later also to formation of nanoparticulate mackinawite (FeS) via H₂S precipitation with Fe^II. Pyrite (FeS₂) was a quantitatively insignificant product of reductive Fe and S mineralization. This study provides important new insights into Fe and S geochemistry in settings where schwertmannite is subjected to reducing conditions.     

The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite

Schwertmannite is a ubiquitous mineral formed from acid rock drainage (ARD), and plays a major role in controlling the water chemistry of many acid streams. The formation of schwertmannite was investigated in the acid discharge of the Monte Romero abandoned mine (Iberian Pyrite Belt, SW, Spain). Schwertmannite precipitated from supersaturated solutions mainly owing to the oxidation of Fe(II) to Fe(III) and transformed with time into goethite and jarosite. In a few hours, schwertmannite precipitation removed more than half of the arsenic load from solution, whereas the concentration of divalent trace metals (Zn, Cu, Pb, Cd, Ni, and Co) remained almost unchanged. In the laboratory, natural schwertmannite was kept in contact with its coexisting acid water in a flask with a solid-liquid mass ratio of 1:5 for 353 days. During this time, the pH of the solution dropped from 3.07 to 1.74 and the concentrations of sulfate and Fe increased. During the first 164 days, schwertmannite transformed into goethite plus H₃O-jarosite but, subsequently, goethite was the only mineral to form. Some of the trace elements, such as Al, Cu, Pb, and As were depleted in solution during the first stage as schwertmannite transformed into goethite plus H₃O-jarosite. On the contrary, the transformation of schwertmannite to goethite (with no jarosite) during the second stage released Al, Cu, and As to the solution. Despite the variation in their concentrations in solution, approximately 80% of the total Al and Cu inventories and more than 99% As and Pb remained in the solid phase throughout the entire aging process.     

Schwertmannite stability in acidified coastal environments

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.     

Arsenate and chromate incorporation in schwertmannite

High concentrations of Cr (up to 812 ppm) and As (up to 6740 ppm) were detected in precipitates of the mineral schwertmannite in areas influenced by acid mine drainage. Schwertmannite may act as well as a natural filter for these elements in water as well as their source by releasing the previously bound elements during its dissolution or mineral-transformation. The mechanisms of uptake and potential release for the species arsenate and chromate were investigated by performing synthesis and stability experiments with schwertmannite.Schwertmannite, synthesized in solutions containing arsenate in addition to sulphate, was enriched by up to 10.3 wt% arsenate without detectable structural changes as demonstrated by powder X-ray diffraction (XRD). In contrast to arsenate, a total substitution of sulphate by chromate was possible in sulphate-free solutions. Thereby, the chromate content in schwertmannite could reach 15.3 wt%.To determine the release of oxyanions from schwertmannite over time, synthetic schwertmannite samples containing varying amounts of sulphate, chromate and arsenate were kept at a stable pH of either 2 or 4 over 1 year in suspension. At several time intervals Fe and the oxyanions were measured in solution and alterations of the solid part were observed by XRD and Fourier-Transform infrared (FT-IR) spectroscopy. At pH 2 schwertmannite partly dissolved and the total release of arsenate (24%) was low in contrast to chromate (35.4–57.5%) and sulphate (67–76%). Accordingly, the ionic activity product (log IAP) of arsenated schwertmannite was lowest (13.5), followed by the log IAP for chromated schwertmannite (16.2–18.5) and the log IAP for regular (=non-substituted) schwertmannite (18). At pH 4 schwertmannite transformed to goethite, an effect which occurred at the fastest rate for regular schwertmannite (=arsenate- and chromate-free), followed by chromate and arsenate containing schwertmannite. Both chromate and more evidently arsenate have a stabilizing effect on the schwertmannite structure, because they retarded the dissolution and transformation reactions.These kinetic investigations as well as crystallographic considerations demonstrated that the strength of the Fe(III) complexes with the anions controls the formation process and the stability of schwertmannite: with increasing affinity of the oxyanions to form complexes with Fe(III), the strength of the resulting binding and thus the stability and substitution preference increases.     

Schwertmannite transformation to goethite via the Fe(II) pathway: Reaction rates and implications for iron-sulfide formation

Schwertmannite (Fe₈O₈(OH)₆SO₄) is a common Fe(III)-oxyhydroxysulfate mineral in acid-sulfate systems, where its formation and fate strongly influence water quality. The present study examines transformation of schwertmannite to goethite (FeOOH), as catalyzed by interactions with Fe(II) in anoxic aquatic environments. This study also evaluates the role of the Fe(II) pathway in influencing the formation of iron-sulfide minerals in such environments. At pH > 5, the rates of Fe(II)-catalyzed schwertmannite transformation were several orders of magnitude faster than transformation in the absence of Fe(II). Complete transformation of schwertmannite occurred within only 3-5 h at pH > 6 and Fe(II)_(aq) ? 5 mmol L⁻¹. Model calculations indicate that the Fe(II)-catalyzed transformation of schwertmannite to goethite greatly decreases the reactivity of the Fe(III) pool, thereby favoring SO₄-reduction and facilitating the formation of iron-sulfide minerals (particularly mackinawite, tetragonal FeS). Examination of in situ sediment geochemistry in an acid-sulfate system revealed that the rapid Fe(II)-catalyzed transformation was consistent with an abrupt shift from an acidic Fe(III)-reducing regime with abundant schwertmannite near the sediment surface, to a near-neutral mackinawite-forming regime where goethite was dominant. This study demonstrates that the Fe(II) pathway exerts a major influence on schwertmannite transformation and iron-sulfide formation in anoxic acid-sulfate systems. These findings have important implications for understanding acidity dynamics and trace element mobility in such systems.     

Formation and stability of schwertmannite in acidic mining lakes

Schwertmannite (ideal formula: Fe₈O₈(OH)₆SO₄) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O₂-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe³⁺ and sulfate, and ii) a redox equilibrium exists between Fe²⁺ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO₄ solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe³⁺ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).     

A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump

At the abandoned As mine in Nishinomaki, Japan, discharged water from the mining and waste dump area is acidic and rich in As. However, the As concentration in the drainage has been decreased to below the maximum contaminant level (0.01 mg/l for drinking water, Japan) without any artificial treatments before mixing with a tributary to populated areas. This implies that the As concentration in water from the waste dump area has been naturally attenuated. To elucidate the reaction mechanisms of the natural attenuation, analysis of water quality and characterization of the precipitates from the stream floor were performed by measuring pH, ORP and electric conductivity on-site, as well as X-ray diffraction, ICP-mass spectrometry and ion-chromatography. Selective extractions and mineral alteration experiments were also conducted to estimate the distribution of As in constituent phases of the precipitates and to understand the stability of As-bearing phases, respectively. The water contamination resulted from oxidation of sulfide minerals in the waste rocks, i.e., the oxidation of pyrite and realgar and subsequent release of Fe, SO₄, As(V) and proton. The released Fe(II) transformed to Fe(III) by bacterial oxidation; schwertmannite then formed immediately. While the As concentrations in the stream were lowered nearly to background level downstream, those in the ochreous precipitates were up to several tens of mg/g. The As(V) was effectively removed by the formed schwertmannite and had been naturally attenuated. Although schwertmannite is metastable with respect to goethite, the experiments show that the transformation of schwertmannite to goethite may be retarded by the presence of absorbed As(V) in the structure. Therefore, the attenuation of As in the drainage and the retention of As by schwertmannite are expected to be maintained for the long term.     

Spatial variability of arsenic in some iron-rich deposits generated by acid mine drainage

Potential contamination of rivers by trace elements can be controlled, among others, by the precipitation of oxyhydroxides. The streambed of the studied area, located in “La Châtaigneraie” district (Lot River Basin, France), is characterised by iron-rich ochreous deposits, acidic pH (2.7–4.8) and SO₄–Mg waters. Beyond the acid mine drainage, the presence of As both in the dissolved fraction and in the deposits is also a problem. Upstream, at the gallery outlet, As concentrations are high (As_max = 2.6 μmol/l and up to 5 wt% locally, respectively, in the dissolved and in the solid fractions). Downstream, As concentrations decrease below 0.1 μmol/l in the dissolved fraction and to 1327 mg/kg in the solid fraction. This natural attenuation is related to the As retention within ochreous precipitates (amorphous to poorly crystalline Fe oxyhydroxides, schwertmannite and goethite), which have great affinities for this metalloid. Upstream, schwertmannite is dominant while downstream, goethite becomes the main mineral. The transformation of schwertmannite into goethite is observed in the upstream deposits as schwertmannite is unstable relative to goethite. Furthermore, thermodynamic calculations indicate that the downstream goethite is not able to precipitate in situ according to the water chemistry. Goethite mainly results from the transformation of schwertmannite and its solid transport downstream.Moreover, as highlighted by leaching experiments carried out on the ochreous precipitates, this transformation does not seem to affect the As-retention in solids as no release of As was observed in the solution. Arsenic may either be strongly trapped by co-precipitation in the present minerals or it may be quickly released and re-adsorbed on the precipitate surface.     

Geochemistry of ochreous precipitates from coal mine drainage in India

The deposition of ochreous is common by a consequence of acid mine drainage (AMD). The ochreous precipitated from the AMD sites around Tertiary coalfield of Assam, India were collected and characterized by X-ray diffractometry (XRD), Fe to S molar ratio, ammonium oxalate acid (pH 3.0) extraction, fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), scanning electron microscope (SEM) and transmission electron microscope (TEM). The ochreous mainly consists of goethite, schwertmannite, ferrihydrite and jarosite. Mineralogy of ochreous was controlled by the pH whereas formation of ferrihydrite was favored at high organic carbon content. Role of bacteria for the formation of secondary minerals was observed. Mobility of metals was controlled by the ochreous, and they were also retained during the process of phase transformation of poorly ordered iron-oxyhydroxysulfates into the stable forms.     

Sedimentary iron geochemistry in acidic waterways associated with coastal lowland acid sulfate soils

We examined the solubility, mineralogy and geochemical transformations of sedimentary Fe in waterways associated with coastal lowland acid sulfate soils (CLASS). The waterways contained acidic (pH 3.26-3.54), Fe^III-rich (27-138 μM) surface water with low molar Cl:SO₄ ratios (0.086-5.73). The surficial benthic sediments had high concentrations of oxalate-extractable Fe(III) due to schwertmannite precipitation (kinetically favoured by 28-30% of aqueous surface water Fe being present as the Fe^III species). Subsurface sediments contained abundant pore-water HCO₃ (6-20 mM) and were reducing (Eh < −100 mV) with pH 6.0-6.5. The development of reducing conditions caused reductive dissolution of buried schwertmannite and goethite (formed via in situ transformation of schwertmannite). As a consequence, pore-water Fe^II concentrations were high (>2 mM) and were constrained by precipitation-dissolution of siderite. The near-neutral, reducing conditions also promoted SO₄-reduction and the formation of acid-volatile sulfide (AVS). The results show, for the first time for CLASS-associated waterways, that sedimentary AVS consisted mainly of disordered mackinawite. In the presence of abundant pore-water Fe^II, precipitation-dissolution of disordered mackinawite maintained very low (i.e. <0.1 μM) S^−II concentrations. Such low concentrations of S^−II caused slow rates for conversion of disordered mackinawite to pyrite, thereby resulting in relatively low concentrations of pyrite (<300 μmol g⁻¹ as Fe) compared to disordered mackinawite (up to 590 μmol g⁻¹ as Fe). This study shows that interactions between schwertmannite, goethite, siderite, disordered mackinawite and pyrite control the geochemical behaviour of sedimentary Fe in CLASS-associated waterways.