Behavior of rare earth elements during mixing of different types of water (Kunashir,the Kurile Islands)

The fractionation of rare earth elements (REE) was evaluated under the conditions of natural acidic water mixing with fresh and sea waters using the example of unique objects on Kunashir Island (the Kislaya and Lesnaya rivers). It was shown that the concentrations and fractionation of REE in the water types considered are diverse and controlled by a number of factors. The concentrations of dissolved REE normalized to the North American Shale Composite show an increase from the light to the heavy REE, which reflects both the character of the REE input with the thermal waters and the more active sorption of the light REE and their preferential removal to suspended solids. This is supported by the similar REE patterns in the suspended matter of the Kislaya River. The mixing of the waters of the Kislaya and Lesnaya rivers, which are assigned to different chemical types, is accompanied by active REE coprecipitation with Fe, Al, and Mn oxides and the more extensive removal of the light REE compared with the heavy REE. During acidic water mixing with seawater, more than 80% of the REE were precipitated at a salinity of 8‰.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Geochemical and hydrogeochemical evolution of groundwater in Ferdows area, northeast of Iran

The chemical analysis of 19 water wells in Ferdows area, Northeastern Iran, has been evaluated to determine the hydrogeochemical processes and ion concentration background in the region. In the study area, the order of cation and anion abundance is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Cl^? > SO ₄ ^?2  > HCO₃ ^? > NO₃ ^?, respectively, and the dominating hydrochemical types are Na–Cl. Most metal concentrations in water depend on the mineral solubility, and pH, Eh, and salinity of the solution. Their ΣREE concentrations showed excellent correlations with parameters such as TDS and pH. North American Shale Composite (NASC)-normalized REE patterns are enriched in the HREEs relative to the LREEs for all groundwaters. They all have positive Eu anomalies (Eu/Eu* = 0.752–3.934) and slightly negative Ce anomalies (Ce/Ce* = 0.019–1.057). Reduction–oxidation, complexation, desorption, and re-adsorption alter groundwater REE concentrations and fractionation patterns. The positive Eu anomalies in groundwaters are probably due to preferential mobilization of Eu²⁺ relative to the trivalent REEs in the reducing condition.     

鄱阳湖流域赣江北支水体和沉积物中稀土元素的含量和分异特征

稀土的开发和广泛应用使得人们倍加关注其在环境中的分布及其环境地球化学行为。赣江作为鄱阳湖流域五大入湖河之一,发源于稀土资源富集的赣南地区,而其下游水体及周边地下水中稀土元素的含量和分异特征目前尚不完全清楚。以赣江北支水体及沉积物为研究对象,开展了稀土元素地球化学研究。结果表明,赣江北支水体中稀土元素总量在地表水中为230~1 146 ng/L(均值458.85 ng/L),地下水中为284~1 498 ng/L(均值634.94 ng/L),沉积物中稀土元素总量为177.9~270.7 mg/kg(均值226.99 mg/kg)。PHREEQC模拟计算表明,水体中的稀土元素主要以碳酸根络合物(REEC0₃⁺)的形式存在。地表水和地下水总体上均表现为重稀土元素相较于轻、中稀土元素富集,沉积物未表现出明显的富集特性;水体具有Ce、Eu负异常特点,而沉积物表现为Ce正异常和Eu负异常,指示氧化还原环境和水岩相互作用对稀土元素在水-沉积物系统中迁移转化的影响。地下水中稀土元素的含量沿流向具有上升趋势,而水体中重稀土元素的富集程度不断减弱,同时碳酸根络合物(REEC0₃⁺)的占比不断降低,反映水体中稀土元素的含量受到pH、胶体吸附、络合作用以及地下水-地表水相互作用的影响。水体中重稀土元素的富集受到碳酸根络合反应的影响,Ce、Eu负异常与Ce氧化沉淀和母岩特性相关。Gd异常值表明,研究区中下游水体中的Gd元素受到人为输入的影响。     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

The behaviour of the rare earth elements during mixing of river and sea waters

Rare earth element concentrations have been measured in organic-rich Luce river water and coastal sea water. Concentrations (e.g. ～350?1850 pmol/kg Nd in the Water of Luce and ～45?350 pmol/ kg Nd in Luce Bay) are related to the presence of particles, with 30–60% of the REE associated with >0.4?0.7 μm particles, and to riverine Fe concentrations. REE fractionation occurs in the river water the submicrometre river water is heavy REE enriched whereas the coarser fraction has a more shale-like REE pattern.Laboratory experiments show that the REE in organic-rich river waters are chiefly associated with Feorganic matter colloids which flocculate during estuarine mixing. Preferential removal of heavy REE (～95%) relative to light REE (～60%) occurs, but no Ce anomaly is developed. In contrast, no REE removal occurs during estuarine mixing with organic-poor river water.     

华北平原高氟地下水中稀土元素分布和分异特征

高氟地下水是世界各国研究者广泛关注的重大环境问题。尽管对高氟地下水的化学特征、形成机理和扩散机制等已有不少研究,但其稀土元素(REE)的含量和分异特征以及这些特征能否反映高氟地下水的形成和分布尚不清楚,这在一定程度上限制了REE在高氟地下水中的运用。本研究以地下水氟离子异常严重地区——华北平原为研究区,沿地下水流向采集浅层和深层地下水样,研究分析了水中氟离子和REE的地球化学特征。浓度分析结果表明地下水氟离子浓度介于0.28 mg/L和9.33 mg/L之间,其中55%超出我国饮用水标准规定值1.0 mg/L;PHREEQC计算结果反映地下水中氟以NaF、CaF⁺、MgF⁺和自由态F^-形式存在,其中自由态F^-含量占主导(85.42%99.39%);高氟地下水主要分布于中部冲积湖积平原以及东部冲积海积平原,60%高氟地下水样分布在180 m深度以下;水化学图件分析结果指示浅层高氟地下水的形成主要受蒸发浓缩作用的控制,而深层高氟地下水是水岩相互作用下的矿物溶解和离子竞争吸附共同作用的结果。研究区地下水REE含量处于pmol/L至nmol/L级别,PHREEQC模拟计算结果表明REE主要以碳酸络合物( {\mathrm{REECO}}_3^{+}和$REE(CO_{3})_{2}^{-})$的形式存在,与氟离子络合的稀土元素(REEF²⁺和 {\mathrm{REEF}}_2^{+})占01.18%;上陆壳(UCC)标准化结果显示,所有地下水均呈重REE(HREE)和中REE(MREE)相对于轻REE(LREE)富集的模式,且具有显著Ce负异常(0.11* = Ce_UCC/(La_UCC×Pr_UCC)^0.5<2.29)特性;地下水富HREE主要归因于HREE比LREE优先与碳酸根络合,并且形成更加稳定的碳酸络合物。沿地下水流向,深层地下水中总REE含量与地下水中氟浓度均呈现不断上升的变化趋势,同时高氟地下水比低氟地下水更易富集重稀土元素,说明稀土元素对深层含水层富氟行为具有一定的指示作用。     

Geochemistry of rare-earth elements in shallow groundwater,northeastern Guangdong Province,China

Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.     

Comparison of the behaviour of rare earth elements in surface waters,overburden groundwaters and bedrock groundwaters in two granitoidic settings,Eastern Sweden

This work, which was done within the Swedish nuclear waste management program, was carried out in order to increase the understanding of the mobility and fate of rare earth elements (REEs) in natural boreal waters in granitoidic terrain. Two areas were studied, Forsmark and Simpevarp, one of which will be selected as a site for spent nuclear fuel. The highest REE concentrations were found in the overburden groundwaters, in Simpevarp in particular (median ∑REE 52 μg/L), but also in Forsmark (median ∑REE 6.7 μg/L). The fractionation patterns in these waters were characterised by light REE (LREE) enrichment and negative Ce and Eu anomalies. In contrast, the surface waters had relatively low REE concentrations. They were characterised either by an increase in relative concentrations throughout the lanthanide series (Forsmark which has a carbonate-rich till) or flat patterns (Simpevarp with carbonate-poor till), and had negative Ce and Eu anomalies. In the bedrock groundwaters, the concentrations and fractionation patterns of REEs were entirely different from those in the overburden groundwaters. The median La concentrations were low (just above 0.1 μg/L in both areas), only in a few samples were the concentrations of several REEs (and in a couple of rare cases all REEs) above the detection limit, and there was an increase in the relative concentrations throughout the lanthanide series. In contrast to these large spatial variations, the temporal trends were characterised by small (or non existent) variations in REE-fractionation patterns but rather large variations in concentrations. The Visual MINTEQ speciation calculations predicted that all REEs in all waters were closely associated with dissolved organic matter, and not with carbonate. In the hydrochemical data for the overburden groundwater in particular, there was however a strong indication of association with inorganic colloids, which were not included in the speciation model. Overall the results showed that within a typical boreal granitoidic setting, overburden groundwaters are enriched in REEs, organic complexes are much more important than carbonate complexes, there is little evidence of significant mixing of REEs between different water types (surface, overburden, bedrock) and spatial variations are more extensive than temporal ones.     

Rare-Earth Elements in the Atmospheric Precipitation of the City of Blagoveshchensk

The mineral composition, distribution and fractionation of rare-earth elements in dissolved and suspended forms (solid residue) of atmospheric precipitation were studied by analyzing the snow sampled over urbanized territory by the example of the city of Blagoveschensk. Electron-microscopic studies revealed the own minerals of rare-earth elements in dust aerosols. It is shown that the main sources of the atmospheric pollution by rare-earth elements were emissions of TPP (heat and power plants) and boiler houses. Contrasting geochemical anomalies of rare-earth elements were found in the snow cover of the city. The REE concentrations in the solid phase of snow are few orders of magnitude higher than those of the liquid phase. The snow solid phase provides insight into the REE behavior, because it directly reflects the impact of different anthropogenic sources. The characteristic feature of the REE distribution in the solid residue of snow is their LREE enrichment relative to MREE and HREE. The average HREE content is 10% of total REE. In the snow water–solid phase system, most samples show weak fractionation between LREE and HREE owing to the low total mineralization of the snow liquid phase and the small content of organic matter.     

深层地下水稀土元素无机形态及其对稀土特征的影响——以皖北任楼矿煤系含水层为例

在对皖北任楼矿煤系含水层地下水常规离子和稀土元素组成分析的基础上,运用Visual Minteq软件对溶解态稀土的无机形态进行了模拟。结果表明:煤系含水层地下水分为富SO₄2-和富HCO₃-(或富CO₃2-)两类,二者pH值大致以8.20/8.36为界。富SO₄2-水具有相对富HCO₃-水偏低的稀土总量,但二者在PAAS(后太古代平均页岩)标准化图解上均表现为轻稀土亏损的型式。富SO₄2-水中稀土无机形态包括Ln3+、LnCO₃+、LnSO₄+、Ln(CO₃)₂-和Ln(SO₄)₂-(Ln代表稀土元素),但富HCO₃-水中以Ln(CO₃)₂-和LnCO₃+为主,且各形态的相对含量与pH值和元素类型(如轻、重稀土)关系密切。HCO₃-含量与地下水∑REE和/Nd_SN/Yb_SN存在明显的相关性,表明不同含量的稀土元素无机形态(尤其是Ln(CO₃)₂-)对地下水中稀土元素总量和轻重稀土分异程度存在影响。      

Colloidal Control on the Distribution of Rare Earth Elements in Shallow Groundwaters

A 7-year monitoring period of rare earth element (REE) concentrations and REE pattern shapes was carried out in well water samples from a 450 m long transect setup in the Kervidy/Coët-Dan experimental catchment, France. The new dataset confirms systematic, topography-related REE signatures and REE concentrations variability but challenges the validity of a groundwater mixing hypothesis. Most likely, this is due to REE preferential adsorption upon mixing. However, the coupled mixing–adsorption mechanism still fails to explain the strong spatial variation in negative Ce anomaly amplitude. A third mechanism—namely, the input into the aquifer of REE-rich, Ce anomaly free, organic colloids—is required to account for this variation. Ultrafiltration results and speciation calculations made using Model VI agree with this interpretation. Indeed, the data reveal that Ce anomaly amplitude downslope decrease corresponds to REE speciation change, downhill groundwaters REE being mainly bound to organic colloids. Water table depth monitoring shows that the colloid source is located in the uppermost, organic-rich soil horizons, and that the colloid input occurs mainly when water table rises in response to rainfall events. It appears that the colloids amount that reaches groundwater increases downhill as the distance between soil organic-rich horizons and water table decreases. Topography is, therefore, the ultimate key factor that controls Ce anomaly spatial variability in these shallow groundwaters. Finally, the <0.2 μm REE fraction ultimately comes from two solid sources in these groundwaters: one located in the deep basement schist; another located in the upper, organic-rich soil horizon.     

新疆乌仑古－斋桑泊构造带晚古生代花岗岩类的稀土元素分布模式

本文选择新疆北部乌仑古－斋桑泊构造带上６个有代表性的花岗岩体，系统进行了岩体地质、显微岩相学、主量元素与稀土元素地球化学研究．根据岩石副矿物类型与主要造岩矿物组成解释了各种岩石类型的稀土配分，根据主量元素－稀土元素相关性闸明了稀土元素在结晶分异过程中的分镏，按照两阶段、不同结晶分异程度模型对各种岩石类型的稀土配分进行了定量模拟；根据不同岩石类型的时空分布及其与构造环境的对应关系探讨了它们的成因。最后，对碱性花岗岩的成因提出了新的解释。     

Analytical Artifacts Associated with the Chelating Resin Extraction of Dissolved Rare Earth Elements in Natural Water Samples

In order to determine rare earth elements (REE) in coastal seawater and groundwater samples using an inductively coupled plasma mass spectrometer, a time-efficient chelating resin column method has been widely used for small water volumes (<100 mL). We obtained improved, quantitative (>95%) results for extracting REE from most of the seawater (including the certified reference materials) and groundwater samples at extraction conditions of pH 5.8–6.0, flow rates <1.2 mL min⁻¹, and 1.2 g of wet resin weight (Chelex 100, Bio-Rad, 7 mm diameter). However, we often encountered large fractionations of HREE (heavy REE) relative to LREE (light REE) associated with chelating resin extraction for some organic-rich coastal seawater samples. This fractionation could be due to unidentified complexation of HREE with natural organic substances in water samples. Our results imply that many previous observations reporting the natural fractionation of HREE using this method could have been misleading. Thus, we suggest that the quantitative (>95%) extraction of REE should be confirmed by using either one of the HREE (i.e., Tm) as a spike or isotope dilution for natural aqueous samples which have large matrix effects.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

Effects of phosphate mining activity on groundwater quality at Wadi Queh, Red Sea, Egypt

The groundwater in Wadi Queh exists in two main hydrogeological units; fractured Precambrian basement and sedimentary rocks with high contribution for groundwater recharge. To study the impacts of phosphate mining activities on the groundwater quality in the area, three groundwater samples that represent all water wells in the area were collected and analysed for major ions and some heavy metals. In addition, three bulk samples representing the phosphatic sediments collected from upstream and downstream of the drainage basin were collected and analysed to understand the source of groundwater contamination. The total concentrations of dissolved solids suggest that the groundwater in the area grades from fresh to brackish water (961–1,580 mg/l), and is characterized by sodium–calcium–sulphate–chloride and sodium–magnesium–sulphate–chloride chemical types. The results showed high concentrations of the heavy metals in well nos. 1 and 2 in downstream parts compared to well no. 3 in upstream part reflecting their influence by the mining activities.     

喀斯特河流溶解态稀土元素组成变化及其控制因素

以化学萃取- 反萃取分离法为手段,结合等离子质谱分析仪测量了喀斯特地区乌江、沅江两大水系的枯水期河流的溶解态稀土元素含量。该两河流的化学组成代表了流经碳酸盐岩地层的河水的化学组成。与世界其它地区低pH的河水不同,喀斯特地区河水溶解态稀土元素含量较低,页岩标准化配分模式并不平坦,轻、重稀土元素分异因河流的不同而不同,乌江水系上游轻稀土元素( LREE)相对重稀土元素( HREE)富集,中下游HREE相对于LREE富集,沅江水系河水HREE相对于LREE富集,页岩标准化配分模式具明显的Ce、Eu负异常。乌江、沅江及其支流有高的溶解盐,含有较高的溶质浓度,河水水化学(高碱度、高离子含量、高pH值)和水/粒相互作用控制了喀斯特河水中溶解态稀土元素的含量和轻、重稀土元素的分异。      

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

江汉平原浅层含砷地下水稀土元素特征及其指示意义

江汉平原被确认为我国南方新的饮水型砷中毒病区,目前对于江汉平原高砷地下水的成因机理研究还有待完善.综合运用水文地球化学分析与PHREEQC地球化学模拟计算,分析了地下水和沉积物中REE分异特征及其沿地下水流向形态变化规律.江汉平原地下水REE含量为0.032~0.843 μg/L,富集LREE,具显著Eu正异常,且地下水中Eu异常与As含量呈正相关关系.地下水中REE形态主要以LnCO₃+及Ln(CO₃)₂-为主,沿地下水流向LnCO₃+降低、Ln(CO₃)₂2-升高.地下水REE浓度分布受到HCO₃-的络合作用及Fe氧化物矿物的还原性解吸附过程控制,径流途径中继承沉积物矿物的REE配分模式及Fe氧化物矿物对LREE的优先解吸附可能是地下水富集LREE的原因,并且沿流向上REE形态分布受到pH控制.研究区中Eu含量及Eu正异常对地下水As富集程度具有一定的指示意义.      

Do Archean chemical sediments record ancient seawater rare earth element patterns?

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)_SN, (Pr/Yb)_SN, (Nd/Yb)_SN, and (Gd/Yb)_SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.