The Heavy Metals Speciations in Bottom Sediments of Vyshny Volochek Reservoir

The water ecosystem of the Vyshny Volochek Reservoir is characterized based on the study of the distribution of heavy metals speciations in the solid phase and pore waters of bottom sediments. Using the sequential extraction procedure, it is shown that Mn is mainly present in exchangeable and carbonate-bound forms; significant roles for Fe, Zn, Pb, and Co are played by forms that are bound to iron and manganese hydroxides and Cu and Ni are mainly bound to organic matter. Thermodynamic calculations have established the prevailing share of the following forms in pore waters: free ions for Zn, Ni, Co, and Cd, carbonate complexes for Pb, and fulvic complexes for Cu. It has been revealed that the speciation forms of heavy metals in bottom sediments depend on the lithological features and content of organic matter in sediments.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

Temporal and spatial variability of trace metals in suspended matter of the Mandovi estuary,central west coast of India

Studies on the suspended particulate matter (SPM) in the Mandovi estuary, western India indicate that during the monsoon and pre-monsoon, the SPM increases, and the major and trace metals decrease from stations in the upstream to downstream of the estuary. SPM is consistently low at all stations during the post-monsoon. Trace metals (Cu, Ni, Zn, Cr, and Pb) show strong inter-relationships. They correlate well with Fe and Mn only during the monsoon. The concentrations of Cr, Cu, and Pb are high during the post-monsoon. Enrichment factors and I _geo values of metals indicate that Mn shows significant to strong pollution in all seasons, while Cr, Ni, and Zn during monsoon, and Cr during the post-monsoon show moderate pollution. SPM is controlled by the turbidity maximum, while major and trace metals are governed seasonally by a combination of river discharge, resuspension, spillage of Fe–Mn particulates, and anthropogenic contamination. Incursion of saline waters deep into the river channel during the dry season facilitates aggregation and settling of particulate-borne pollutants close to the discharge area, thereby keeping the estuarine waters free from major contamination.     

广东三水盆地古近系心组生油层的元素地球化学特征

沉积物的元素地球化学特征是对沉积盆地水体环境以及古气候条件变化的响应。本文根据元素（Al、Fe、Mg、Ca、K、Na、P、V、Ni、Co、Cr、Cu、Zn、Sr、Ba、Cd、Li、Mn、Pb、Ti）的含量及其比值（Al/Ti、Fe/Mn、Sr/Ba、Mg/Ca、Sr/Ca、Na/Ca、V/Cr、Ni/Co、Ni/V）的变化，对三水盆地古近系心组红岗段生油层的沉积条件进行了系统分析。心组红岗段下部（亚段A）表现为较稳定的地球化学特征。各元素丰度及其比值指示这一时期陆源输入持续较高、且物源组成变化不大。由于海水入侵的影响，湖盆水体盐度相对较高，底部水体以弱氧化条件为主，O₂-H₂S界面位于水/沉积物界面附近。红岗段中上部（亚段B、C）的元素地球化学特征变化较为频繁且幅度很大，反映古气候和湖盆沉积条件的迅速变迁。在潮湿气候条件下，沉积物的地球化学特征表现为以Al、Ti为代表的外源元素含量及其比值较高，而Mg、Ca等盆内化学沉积元素含量较低。古氧气指标指示底部水体为还原环境，有利于有机质保存。因而，相应于较高的有机碳含量。在间歇性干旱时期，陆源输入减少，外源元素含量及其比值显著降低。随着蒸发作用的加强，水体盐度加大，内源元素丰度以及Mg/Ca、Sr/Ba、Sr/Ca和Na/Ca比值大幅度上升。底部水体为氧化环境，O₂-H₂S界面多位于水/沉积物界面或沉积物中。上述两种气候条件在红岗段中上部沉积时期交替出现。红岗段沉积后期由于淡水的长期输入，湖水出现逐渐淡化趋势。     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

Temporal and spatial distribution of dissolved Cu, Ni and Zn in the coastal waters of Jeddah, eastern Red Sea

Dissolved Cu, Ni, and Zn were measured in the surface coastal waters of Jeddah, eastern Red Sea during October 2004 and April 2005. High values of trace metals, particularly Zn, were recorded in the Southern Corniche area close to a sewage effluent indicating a significant contribution from the wastewater. Concentrations of trace metals decreased northward and southward under the effect of dilution. Another hot spot was also observed in the vicinity of Jeddah Desalination Plant (JDP) during April 2005 indicating a possible contribution from the JDP to trace metal contents in the study area. Trace metals were correlated to salinity, nutrients and particulate organic carbon (POC). The good association between Zn and reactive silicate and Ni and ammonium is attributed to simultaneous biological utilization and regeneration. The behavior of copper suggested adsorption of Cu onto the POC during October 2004 whereas in April 2005 the most important process seems to be desorption of Cu from the particulate materials.     

Occurrence, distribution and probable source of the trace elements in ghugus coals, wardha valley, districts chandrapur and yeotmal, maharashtra, India

Trace-element determinations of 15 coal samples have been made in order to know their distribution, behaviour and associations with the organic and inorganic fractions in the coal. The coal samples have been systematically collected in stratigraphic sequences so that the vertical variation of the trace-elements can be studied. The elements determined by spectographic analysis are W, V, Cr, Sc, Y, Cu, Co, Pb, Be, Ni and Ba. The results indicate that the concentration of trace elements in these coals varies greatly from bottom to top sections. The elements V and Co are extremely poor in the top and middle sections, whereas in the bottom section they are fairly distributed. Be is extremely poor in the bottom section, and fairly distributed in the middle and top sections. W, Sc, Y have poor concentration in the bottom section as compared to the middle and top sections. Ni is fairly distributed in the bottom section whereas its concentration is poor in the middle and top sections. Cr and Cu are fairly distributed in the bottom, middle and top sections. Ba has unusually high concentration in all the sections.It appears from the present study that W, Cr, Sc, Y and Be are concentrated more in silicate minerals (clay, quartz, etc.) associated with coal, and the elements like , Co, and Ni have intimate relation with organic matters in coal and are present as organometallic compounds as well as absorbed cations. Cu and Pb which are present in the coals are derived from the inorganic matter, mainly from the pyrites, whereas W has affinity with carbonate minerals in the coals. The Ba is mainly associated with the inoraanic matter of coal; its unusually high concentration indicates association with carbonates, clays and other silicate minerals.     

海平面变化在湖南西部桑植地区栖霞组富有机碳沉积物形成中的作用

湖南西部桑植地区中二叠统栖霞组地层旋回性明显,有机质也呈周期性变化.研究其有机质聚集堆积控制因素将有助于理解海平面变化在富有机碳沉积物形成过程中的作用.选择其中一个旋回作为研究目的层段,通过黄铁矿形态以及地球化学参数有机碳TOC、硫同位素、DOP以及微量元素的研究发现,初级生产力参数Ba、Ni、Cu和Zn的变化与TOC含量的变化一致,有机质聚集堆积主要受海洋表层初级生产力的控制,底部水体氧化还原条件与初级生产力有关.有机质的堆积最终归因于高频相对海平面变化,海平面快速上升带来丰富的营养物质,提高海洋表层生物生产力,海底有机质的分解消耗大量氧气,氧需求量的增加形成底部水体贫氧-厌氧环境.      

Mineralogical and geochemical indicators of anoxic sedimentation conditions in local depressions within the Sea of Okhotsk in the late Pleistocene-Holocene

This paper reports specific mineralogical and geochemical characteristics of deposits from the local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for the presence of hydrogen sulfide in bottom waters. The deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in the elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U) but have higher Mn contents.     

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu²⁺ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.     

Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.     

Experimental Research on the Photodegradation of the Organic Compounds of Natural Waters

The photodegradation of organo-mineral complexes in natural conditions was studied using samples of soil and swamp waters to study the effect of sunlight on the composition and properties of organic matter and metal forms dissolved in natural waters. The total contents of certain aliphatic and aromatic carboxylic acids increased in the samples after irradiation. Photodegradation of organic matter of the natural waters with the high Fe content is accompanied by the formation of colloidal particles (Fe hydroxides). The number of negatively-charged complexes of Ni, Cu, Zn, and Cd increased under insolation in swamp waters and decreased in soil waters.     

A mid-late Holocene sapropelic sediment unit from the southern Marmara sea shelf and its palaeoceanographic significance

A sapropelic layer, having an age of ca 4750 and 3500 ¹⁴C y BP, was discovered at 0.90–2.35 m below the sea floor (mbsf) in gravity cores from the southern shelf of the Marmara Sea. It is a 15–50 cm thick, phosphorescent green to grey, plastic, clayey hemipelagic mud horizon, containing 1.5–2.9% organic carbon (C_org). The increase in C_org and biogenic carbonate, together with a rich planktonic foraminiferal fauna, indicate increased organic productivity and warm surface waters during the deposition of the sapropelic layer. The down-core profiles of Mn, Fe, Cu, Zn, Pb, Cr, Ni and Co suggest that the sapropelic layer was deposited through an essentially oxic water column. The benthonic foraminiferal fauna indicates reduced oxygen levels in bottomwaters. The sapropelic unit was deposited during a high stand of global sea level. Its deposition was initiated by a large input of terrestrial organic matter and nutrient-rich fresh waters under a relatively warm and wet climate. The fresh water supply caused a strong water stratification, which, in turn, together with high organic matter input, resulted in reduced oxygen levels in the bottomwaters.     

渤海西部表层沉积物中重金属的环境地球化学特征

为探讨渤海西部在多重环境因素变化下沉积物中重金属的环境地球化学行为,分析了渤海西部44个站位表层沉积物样品中8种重金属元素含量,研究了重金属元素的分布特征、环境影响因素及其生态风险。结果表明,渤海西部表层沉积物中As、Cu、Cd、Cr、Hg、Ni、Pb、Zn的平均含量分别为117 mg/kg、255 mg/kg、014 mg/kg、689 mg/kg、0037 mg/kg、303 mg/kg、223 mg/kg、757 mg/kg;Cu、Cr、Ni、Zn含量与有机碳含量、小于63 μm细粒沉积物呈显著正相关,其在表层沉积物中的分布明显受到有机质含量和沉积物粒径的控制,而As、Hg分布没有明显受到有机质含量的影响。富集系数显示,Cr、Ni、Pb和Zn为无富集,Cu、As为轻度富集,Cd和Hg为中度富集。与多种背景值和一致性沉积物质量基准相比较,渤海西部表层沉积物Pb、Cd的含量超出背景值,而Cu、Zn、Ni、Cr、As、Hg含量也存在一定的异常,但其含量水平引发有害生物效应的可能性不大,尽管重金属元素含量偏高,但生态风险较小。     

Interstitial water – sediment geochemistry of N, P and Fe and its response to overlying waters of tropical estuaries: a case from the southwest coast of India

 The concentrations of N, P and Fe in surface sediments and interstitial and overlying (bottom and surface) waters of the Ashtamudi estuary located in the southwest coast of India are reported along with the various chemical species of N (NO₂–N, NO₃–N, NH₃–N and total N) and P (organic P, inorganic P and total P) in interstitial and overlying waters and discussed in terms of the physico-chemical environment of the system. The interstitial water exhibits higher salinity values compared to bottom and surface waters, indicating the coupled effects of salt-wedge phenomena and gravitational convection of more saline-denser marine water downward through surface sediments. N, P and Fe as well as their chemical forms are enriched in the interstitial water compared to bottom and surface waters. However, the dissolved oxygen (DO) shows an opposite trend. The marked enrichment of NH₃–N in the interstitial water and its marginal presence in bottom and surface waters, together with the substantial decrease in the DO concentrations of bottom water and consequent increase in the concentrations of NO₂–N and NO₃–N in interstitial and bottom waters, points to the nitrification process operating in the sediment-water interface of the Ashtamudi estuary. The enrichment of total N, P and Fe in the interstitial water compared to the overlying counterparts and the positive correlation of sediment N, P and Fe with mud contents as well as organic carbon indicate that these elements are liberated during the early diagenetic decomposition of organic matter trapped in estuarine muds. Received: 5 Oktober 1998 · Accepted: 9 February 1999     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Effect of municipal wastewaters on bottom sediment geochemistry and benthic foraminifera of two Red Sea coastal inlets, Jeddah, Saudi Arabia

Al-Arbaeen and Al-Shabab inlets are two Red Sea coastal inlets lying on the mid-coast of Jeddah City, Saudi Arabia. Forty-four surface sediment samples were collected from these inlets and surrounding areas during June 2010. Water depths and the overlying environmental parameters (temperature, salinity, pH and dissolved oxygen) of these samples were measured. Sediment samples were analyzed for variables, such as loss on ignition (LOI, organic matter), CaCO₃, heavy metals (Fe, Mn, Cu, Zn, Cd, Ni, Cr and Pb) and benthic foraminifera to assess any changes in the environment of the inlets and surrounding areas. Variables distribution patterns indicated that mud sediments dominated the inlets and enriched by LOI, heavy metals and Ammonia tepida–Quinqueloculina seminula assemblage, whereas coarse (sand–gravel) sediments dominated the substrates of surrounding areas and enriched by CaCO₃ and Coscinospira hemprichii–Peneroplis planatus–Varidentella neostriatula assemblage with low values of LOI and heavy metals. Highest concentrations of Cu, Zn, Cd, Ni, Cr and Pb were recorded inside the inlets, especially near the discharge points, and they were positively correlated with the LOI and mud fraction indicating their affinity to anthropogenic materials. However, highest concentrations of Fe and Mn were typically recorded in the whole study area. These metals were positively correlated with the LOI values of the surrounding area, but in the inlets they were negatively correlated with the LOI, indicating an existence of reducing conditions caused by limited dissolved oxygen conditions at bottom waters of the inlets. Changing the environment within the inlets, according to higher concentrations of heavy metals and LOI, is probably responsible for the existence of the low density and diversity of benthic foraminifera and the absence of (reefal) symbiont-bearing species.     

Contribution of organic complexation to Ni,Co and Cu speciation in surface waters: Implications for hydrogeochemicalsurveys

Organic materials dissolved in surface waters have long been implicated in metal binding and transport. In particular, fulvic and humic acids are considered to have a significant impact on speciation, total metal levels in solution and on the persistence of those metals. This work emphasizes the role played by dissolved organic matter (DOM) on the complexation of nickel, copper and cobalt and on its application to interpretation of surface water hydrogeochemical survey data. Waters from a number of well-known mining districts in Canada have been studied; in particular from Cobalt (Ontario), Sackville (New Brunswick) and Thetford Mines (Quebec). The diafiltration binding technique was used and shows that nickel, copper and cobalt are complexed significantly by DOM in natural waters. The tendency towards complexation was found to be Cu > Ni > Co. The binding functions determined were observed to be highly sensitive to pH and ligand:metal ratios; a gradation of binding site strength is evident.Data from some hydrogeochemical surveys conducted in the Kenora, Algoma and Ottawa districts of Ontario have been reinterpreted in the light of available data on the complexation behaviour of nickel, copper and cobalt. Occurrence of large water-borne anomalies unsupported by lake sediment loadings is most likely for cobalt and nickel and least likely for copper according to both field observations and experimental data. These studies provide good evidence for the formation of strong solution stable metal-organic species; the principal differences in persistence and migration behaviour are probably due to rates of coagulation and adsorption-precipitation processes which preferentially remove copper from solution. It is fair to conclude that these metals can be of use in mineral exploxation surveys using surface waters provided caution is exercised in interpretation of anomalies, especially in the absence of supporting sediment anomalies. Dissolved organic matter concentrations should always be determined when nickel, copper and cobalt are to be employed.     

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).