Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA

In the present study, the BCR (Community Bureau of Reference) sequential procedure has been applied to determine the zinc partition in sediments taken from a river situated in the Southwest of Romania, in a region subject of intense mining activities. The sampling was performed during three sampling expeditions, organized in the spring, summer, and autumn, 2007. The zinc concentration in different fractions was normalized, its concentration being related to the concentrations of some metals (such as Al or Fe) that are naturally present in sediments. The zinc-contaminated sediments from the investigated area have been evaluated by means of combining the analysis data from the BCR sequential extraction with the normalization to the Al content. The most important zinc collector in the samples taken during the three sampling expeditions is the easily soluble fraction, next being amorphous iron and manganese hydrated oxides fraction, followed by organic matter fraction.     

Heavy metals in bottom sediments of Lake Umbozero in Murmansk Region, Russia

Sediment cores collected from different locations of Lake Umbozero were studied with respect to concentration and mobility of trace and heavy metals Co, Cu, Fe, Mn, Ni, Pb, U, and Zn. Lake Umbozero is the second largest lake in the Murmansk Region and subjected to contamination by air-borne emissions and river transportation from the nearby metallurgical and mining industries. Unlike its neighboring, more industry-prone Lake Imandra, Lake Umbozero is relatively unexplored with respect to its state of pollution. In our study, metal distribution in sediments was found to vary with respect to the cores, although in general the concentrations were at the same level throughout the lake indicating uniform horizontal distribution of metals. When compared to Lake Imandra, the concentrations of most of the metals studied were significantly lower and represented the levels in sediments measured in lakes of Kola Peninsula located further off from industrial pollutant sources. An exception was Pb the concentration of which was at the same level as in Lake Imandra, probably due to long-distance transport. Sediment layers were subjected to four-step sequential extraction procedure to reveal the metal distribution in soluble, exchangeable, acid-soluble, and residual fractions. Indicative of their potential higher lability, Mn, U, and Zn were generally found in exchangeable fraction; as also Mn and U extensively in the acid-soluble fraction.     

洪泽湖沉积物中磷的形态研究

采用改进的七步连续提取法对洪泽湖9个采样点沉积物中的各形态磷进行了分析,结果表明,所测洪泽湖沉积物中总磷(TP)含量范围为580.7～1 447.7 mg/kg,无机磷(IP)是TP的主要部分,占TP含量的64.32％～88.60％;有机磷(0P)占TP的11.40％～35.68％.受河流注入和人为活动的影响,TP、I...     

Risk assessment of trace metals in an extreme environment sediment: shallow,hypersaline, alkaline,and industrial Lake Acıgöl,Denizli, Turkey

The major and trace element component of 48 recent sediment samples in three distinct intervals (0–10, 10–20, and 20–30 cm) from Lake Ac?göl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the <?60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Ac?göl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.     

Accumulation and remobilization of metals in superficial sediments in Tianjin, China

The concentrations of Cr, Ni, Cu, Zn, Cd, and Pb in superficial sediment samples collected from three representative sites (Yuqiao Reservoir, Haihe River, and Haihe River Estuary) in Tianjin, North China, were analyzed using various single extraction and sequential extraction procedures to determine their remobilization, extractability, and distribution patterns. Sediments from the Haihe River had higher metal concentrations and geo-accumulation indices, especially for Cd and Zn, than sediments from the other two sites, suggesting that the Haihe River has been heavily influenced by anthropogenic activities. In addition, over 31% and 28.2% of the total Cd in the Haihe River and the Yuqiao Reservoir, respectively, and 18.2% of the total Zn in the Haihe River were found to be associated with the exchangeable form, indicating the significant remobilization of Cd and Zn when compared with Cr and Ni. However, over 98% of the Ni and 78% of the Cr were most closely associated with the residue and oxidizable fractions, which resulted in their becoming environmentally immobile. Based on the Environmental Protection Agency method 3050B, Cd and Zn had the greatest extraction efficiency when a single extraction procedure using 0.5-mol L^???1 HCl, 0.43-mol L^???1 HAcO, and 0.05-mol L^???1 ethylene-diamine-tetra-acetic acid was conducted, with extraction yields of up to 72%, 68%, and 56% for Cd and 50%, 49%, and 29% for Zn, respectively, being obtained for the Haihe River sediments. This was followed by the yields of Cu and Pb and, finally, those of unpolluted metals such as Cr and Ni. HCl and acetic acid extraction provided equivalent information for predicting Cd and Zn mobility in the sediments studied and produced suitable results for quick screening.     

Metal speciation studies in the aquifer sediments of Semria Ojhapatti,Bhojpur District,Bihar

The pollution of aquifer sediments by heavy metals has assumed serious concern due to their toxicity and accumulative behavior. Changes in environmental conditions can strongly influence the behavior of both essential and toxic elements by altering the forms in which they occur and therefore quantification of the different forms of metal is more meaningful than total metal concentrations. In this study, fractionation of metal ions in aquifer sediments of Semria Ojhapatti area, Bhojpur district, Bihar has been studied to determine the ecotoxic potential of metal ions. The investigations suggest that iron, copper, and arsenic have a tendency to remain associated in the following order residual > reducible > acid-soluble > oxidizable; manganese and zinc have tendency to be associated as residual > acid-soluble > reducible > oxidizable. The risk assessment code reveals that manganese and zinc occur in significant concentration in acid-soluble fraction and therefore comes under the high risk category and can easily enter the food chain. Most of the iron, copper, and arsenic occur as immobile fraction (i.e. residual) followed by its presence in reducible fraction and would pose threat to the water quality due to changing redox conditions. The metal enrichment factor in the study area shows moderate to significant metal enrichment in the aquifer sediments which may pose a real threat in near future. The geo-accumulation index of metals also shows that the metals lie in the range of strongly contaminated (for iron at shallow depths) to moderately contaminated to uncontaminated values.     

Cadmium partition in river sediments from an area affected by mining activities

In this paper, the cadmium distribution in Certej River sediments in an area seriously affected by intense mining activities has been studied. The main objective of this study was the evaluation of partition of this metal into different operational defined fractions by sequential extractions. Community Bureau of Reference (BCR) sequential extraction was used to isolate different fractions. The sediment quality was assessed both upstream and downstream the pollution input points, along the Certej River, in order to reveal a possible accumulation of cadmium in sediments and the seasonal changes in cadmium concentrations in BCR sediment phases. Our results reveal that most of the cadmium content is divided between both the soluble and iron and manganese hydrated oxide fractions. Based on total cadmium concentrations in sediments, the enrichment factors were estimated using aluminum as normalizing element and the regression curve Cd/Al corresponding to the geochemical background of the studied area.     

A complex investigation of the extent of pollution in sediments of the Sava River. Part 1: Selected elements

The Sava River is the biggest tributary to the Danube River. As a part of the 6th FW EU project, Sava River Basin: Sustainable Use, Management and Protection of Resources (SARIB), ecological status of sediments was investigated. In order to assess the geographical distribution in sediment contamination of the Sava River, inorganic and persistent organic pollutants were analyzed in sediments at 20 selected sampling sites along the Sava River from its spring to its outfall into the Danube River. For comparability of data to other river basins the sediment fraction below 63 μm was studied. Due to complexity of the work performed, the results are published separately (“Part I: Selected elements” and “Part II: Persistent organic pollutants”). In the present study, the extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions and anthropogenic inputs of elements to sediments. To assess the mobile metal fraction extraction in 0.11 mol L^???1, acetic acid was performed (first step of the Community Bureau of Reference extraction procedure), while anthropogenic inputs of elements were estimated on the basis of normalization to aluminum (Al) concentration. According to the Water Framework Directive, the following elements were investigated in sediments: cadmium (Cd), lead (Pb), nickel (Ni), and mercury (Hg). Furthermore, copper (Cu), zinc (Zn), chromium (Cr), arsenic (As), and phosphorous (P) were determined. The analyses of sediments demonstrated slightly elevated values for Hg, Cr, and Ni in industrially exposed sites (concentrations up to 0.6, 380, and 210 mg kg^???1, respectively). However, the latter two elements exist in sparingly soluble forms and therefore do not represent an environmental burden. P concentrations were found in elevated concentrations at agricultural areas and big cities (up to 1,000 mg kg^???1).     

Trends of total cadmium, copper, and zinc in the zebra mussel (Dreissena polymorpha) along the upper reach of the St. Lawrence River: 1994—2005

This study examines spatial and temporal variability of bioaccumulation of cadmium, copper, and zinc in tissues of zebra mussels in the upper reach of the St. Lawrence River which originates at the outflow of Lake Ontario. It was hypothesized that concentrations of these metals in mussel tissues would decline over time and decrease with increasing distance from the outlet of Lake Ontario as a result of on-going efforts to reduce contaminant discharges into the lake. Size of mussels was also evaluated as a factor influencing bioaccumulation. Mussels were collected annually in October from six sites from 1994 to 2005, including one site near a local industry. Individuals were grouped into five or more size classes per site in each year. Soft tissues were analyzed for total cadmium, copper and zinc. Concentrations of cadmium and copper in tissues varied significantly both spatially and temporally. Cadmium concentrations were elevated at most sites; copper concentrations were moderately elevated compared with other studies in the Lake Ontario basin and St. Lawrence River. Zinc showed the most uniformity in mussels possibly due to internal regulation and to low levels of environmental exposure. Animal size correlated with copper concentrations of tissues in approximately 30% of samples but infrequently for cadmium and zinc. Cadmium and copper levels were found to decline downstream over time. Inter-annual variability of metal concentrations in mussel tissues suggests utilization in long-term monitoring programs to discern significant trends.     

Arsenic and trace metals in river water and sediments from the southeast portion of the Iron Quadrangle, Brazil

The Iron Quadrangle has been one of the most important gold production regions in Brazil since the end of the seventeenth century. There, arsenic occurs in close association with sulfide-rich auriferous rocks. The most abundant sulfide minerals are pyrite and arsenopyrite, yet trace metal sulfides occur in subordinate phases as well. Historical mining activities have been responsible for the release of As and trace metals to both aquatic and terrestrial environments close to mining sites in the region. Therefore, this study was aimed to evaluate the distribution and mobility of As, Cd, Co, Cr, Cu, Ni, Pb, and Zn in streams in the southeast portion of the Iron Quadrangle between the municipalities of Ouro Preto and Mariana, the oldest Brazilian Au mining province. Total concentrations of some trace metals and arsenic in water were determined. The four-stage sequential extraction procedure proposed by the commission of the European Communities Bureau of Reference (BCR) was used to investigate the distribution of these elements in stream sediments. Arsenic concentration in water was >10 ??g L^???1 (maximum limit permitted by Brazilian environmental regulations for water destined for human consumption) at all sampling sites, varying between 36.7 and 68.3 ??g L^???1. Sequential extraction in sediments showed high concentrations of As and trace metals associated with easily mobilized fractions.     

Heavy metals in Yeniçağa Lake and its potential sources: soil,water, sediment,and plankton

The distribution and accumulation of heavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Ba, Pb) in the water, sediments, plankton of Yeniça?a Lake, and its potential sources (creeks, sewage, artesian well, soil) were investigated during 1-year study period as monthly or seasonally. Element analyses were performed by ICP–MS. Results showed that the trace and toxic elements (Al, As, Mn, Pb, Fe) concentration in lake water and/or its feeding sources were above the recommended water standards (WHO, EC, EPA, TS-266). It was found that the maximum accumulation of the heavy metals iron, aluminum, manganese, zinc, and barium in the sediment of Yeniça?a Lake. The accumulation order of trace metals were Fe > Al > Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn > Cd in the lake, creeks sediment, and soil samples. The similar results suggest that the accumulation of heavy metals in the sediment is a natural process. Metals accumulated in the lake are naturally mixed from the soil. However, the presence of heavy metals in the analysis of artesian well water and sewage reveals that the transportation occurs also from the groundwater to the lake. The results obtained in plankton in Yeniça?a Lake showed that aluminum, iron, manganese, zinc, and barium were most accumulated elements in the plankton. The lower averages of lead prevalent in the water and sediment during some months were seen to have a significant mean accumulation in the plankton.     

Metal fractionation study on bed sediments of Hussainsagar Lake, Hyderabad, India

Hussainsagar Lake in the heart of Hyderabad City (India) receives toxic substances through five streams draining from a catchment area of 245 km². Of particular interest are heavy metals received from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the lake get adsorbed onto the suspended sediments, which eventually settle down in the bottom of the lake. In this study, fractionation of metal ions has been studied on the bed sediments of Hussainsagar Lake in order to determine the ecotoxic potential of metal ions. Comparison of sediments with average shale values indicated anthropogenic enrichment with copper, nickel, lead, cadmium, and zinc. The risk assessment code as applied to the present study reveals that 10–17% of manganese, 10–18% of nickel, 14–24% of chromium, 10–19% of lead, 21–30% of cadmium, and 18–28% of zinc exist in exchangeable fraction and, therefore, comes under medium risk category and may enter into food chain. The association of these metals with the exchangeable fraction may cause deleterious effects to aquatic life. The present database will help in formulating guidelines for carrying out dredging operations under restoration programs in the Hussainsagar Lake.     

Statistical comparison of heavy metal concentrations in various louisiana sediments

The use of statistical t tests were used to determine lead, zinc, and cadmium enrichment in various Louisiana sediments. Both absolute metal concentrations and trace metal/conservative metal concentration ratios were used in comparing sampled sites to a 110 m deep background core taken just off the mouth of the Mississippi River. Concentration ratios were used to reduce the effects of certain chemical and physical sediment characteristics on the quantity of metal contained in a given sediment.Results from the comparison of sample sites to the background reveal metal enrichment at several sites. The University Lake sampling sites exhibit both lead and zinc enrichment when using both the concentration alone and ratio methods of comparison. Additionally, cadmium enrichment is indicated in the sediments of University Lake when using only the ratio method of comparison. Several sampled sediments in and around the New Orleans metropolitan area exhibited lead and cadmium enrichment.     

Seasonal and spatial distribution of trace elements in the water and sediments of the Tsurumi River in Japan

The Tsurumi, a class-one Japanese river, has a significant metal loading originating from urban environment. Water and sediment samples were collected from 20 sites in winter and summer, 2009 and were analyzed to determine and compare the extent of different trace element enrichment. A widely used five-step sequential extraction procedure was also employed for the fractionation of the trace elements. Concentrations of zinc, copper, lead, chromium, and cadmium were three to four times higher than that of reference values and downstream sediments are much more polluted than the upstream sites. Geochemical partitioning results suggest that the potential trace metal mobility in aquatic environment was in the order of: cadmium > zinc > lead > copper > cobalt > chromium > molybdenum > nickel. About 80.2% zinc, 77.9% molybdenum, 75.3% cobalt, 63.7% lead, 60.9% copper, 55.1% chromium, and 39.8% nickel in the sediment were contributed anthropogenically. According to intensity of pollution, Tsurumi river sediments are moderately to heavily contaminated by zinc, lead, and cobalt. Enrichment factor values demonstrated that zinc, lead, and molybdenum have minor enrichment in both the season. The pollution load index (PLI) has been used to access the pollution load of different sampling sites. The area load index and average PLI values of the river were 7.77 and 4.93 in winter and 7.72 and 4.89 in summer, respectively. If the magnitude of pollution with trace metal in the river system increases continuously, it may have a severe impact on the river’s aquatic ecology.     

Elemental composition of sediments in Lake Jinzai, Japan: Assessment of sources and pollution

Bottom sediments from Lake Jinzai in southwest Japan were analyzed to determine their chemical compositions and to assess the potential for ecological harm by comparison with sediment quality guidelines. The pollution status of lake sediments was evaluated by employing contamination factor (CF), pollution load index (PLI), and geoaccumulation index (I(geo)), focusing on a suite of elements in lakebed and core sediments. Elevated concentrations of As, Pb, Zn, Cu, TOC, N, and P were present in several layers of the upper core and other surface sediments. The elevated metal concentrations are likely related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter, and possibly minor non-point anthropogenic sources. Moreover, correlations between the concentrations of trace metals and organic carbon, nitrogen, phosphorus, and iron, suggest that these elements play a role in controlling abundances. Calculated CF, PLI, and I(geo) indicate that the sediments are strongly polluted with respect to As, moderately to strongly polluted with Zn, and moderately polluted with Pb and Cu. Metal concentrations exceed the New York State Department of Environmental Conservation (NYSDEC) lowest effect level and the Canadian Council of Ministers of the Environment (CCME) interim sediment quality guidelines that indicate moderate impact on aquatic organisms in the study area.     

PBDE,HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy)

The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment’s current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.     

Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Heavy metal concentrations in water and sediments in Tasik Chini, a freshwater lake, Malaysia

The purpose of this paper are to determine the concentration of heavy metals namely cadmium (Cd), copper (Cu) and lead (Pb) in water and sediment; and to investigate the effect of sediment pH and sediment organic matter on concentration of cadmium, copper and lead in sediment at oxidation fraction. For this purpose the concentration of heavy metals were measured in water and sediments at 15 sites from Tasik Chini, Peninsular Malaysia. The sequential extraction procedure used in this study was based on defined fractions: exchangeable, acid reduction, oxidation, and residual. The concentration of heavy metals in residual fraction was higher than the other fractions. Among the non-residual fractions, the concentration of heavy metals in organic matter fraction was much higher than other fractions collected from all sampling sites. The pH of the sediment in all sites was acidic. The mean pH ranges from 4.8 to 5.5 with the higher value observed at site 15. Results of organic matter analysis showed that the percentage of organic matter present in sediment samples varies throughout the lake and all sites of sediments were relatively rich in organic matter ranging from 13.0% to 34.2%. The highest mean percentage of organic matter was measured at sampling site 15, with value of 31.78%.     

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe?CMn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.