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).     

上海市黄浦江表层沉积物重金属污染评价

用沉积物富集系数法和Hakanson潜在生态风险评估法对上海市黄浦江表层沉积物重金属含量进行了评价。结果显示,沉积物中Cd、As和Pb含量富集程度较低,Hg和Cu含量富集程度较高;其分布特征为上游段含量相对较轻,到中游段有所上升,至下游段含量又有所下降,整体呈钟型分布,重金属含量分布规律可能与苏州河对黄浦江下游沉积物的影响和黄浦江中游段有工业污染排放输入有关;河口与内陆河流沉积物中重金属含量存在差异性,河口重金属含量明显下降;调查区37.5%的断面Hg含量潜在生态危害为中等;沉积物富集系数法可用来评价重金属累积程度,而潜在生态风险指数则突出对生物有很强毒性的重金属作用。     

徐州市地表水体底泥重金属污染特征研究

文章对徐州市地表水体底泥重金属的污染特征进行了研究。对流经徐州市的四条主要河流和云龙湖的55个底泥采样点的重金属含量进行了测试,并采用单因子污染指数法进行了评价。结果表明,徐州市地表水体除云龙湖之外均不同程度地受到了重金属元素的污染。荆马河污染最为严重,其次是奎河、故黄河、京杭大运河。云龙湖的第五个采样点也受到了Hg的污染。污染元素的种类及污染程度与徐州市的产业结构密切相关。     

Distribution, accumulation and mobility of mercury in superficial sediment samples from Tianjin, northern China

Seventeen sediment samples at three representative sites (the Yuqiao Reservoir, the Haihe River and the Haihe River Estuary) in Tianjin, northern China, were analyzed to investigate the pollution status, accumulation and mobility of mercury (Hg). The results show that the Haihe River has to be considered as moderate to strongly contaminated with Hg (2 < mean I(geo) = 2.35 < 3), where total Hg contents were ca. 3 to 24 orders of magnitude greater than the regional background value. The sediments collected near a coal-fired power plant in an urban area were found to have very high Hg concentrations, which were significantly related to Hg emissions from coal-fired utility boilers. In the Yuqiao Reservoir, the surface sediments have to be considered as unpolluted with Hg (mean I(geo) = -0.05 < 0) and the Haihe River Estuary sediments have to be considered as unpolluted to moderately polluted with Hg (0 < mean I(geo) = 0.18 < 1). Sediment-bound Hg in the Yuqiao Reservoir and the Haihe River Estuary was found to be predominantly associated with the organo-chelated phase of the sediment (38.3% and 50.5%, respectively). However, unlike the Yuqiao Reservoir and the Haihe River Estuary, Hg in the Haihe River sediments existed mainly as sulfide Hg and elemental Hg, which accounted for 54.2% and 30.7% of total Hg, respectively. The availability of this element seemed restricted. The majority of Hg contamination in the Haihe River sediments had been attributed to historic and modern atmospheric deposition and Hg released from the Haihe River sediments didn't seem to be an important pollutant pathway into the Haihe River Estuary. The results provide new insights into Hg contamination in this region.     

Trace elements as tracers of environmental pollution in the canal sediments (alluvial formation of the Danube River, Serbia)

The purpose of this study was to examine the levels of trace elements and to discuss the origin and mobility of these contaminants in the canal sediments (alluvial formation of the Danube River). The most significant fractions binding all of the studied elements were oxides and silicates. The high proportion of elements in the residual fraction and the generally low contents of extractable elements reflected the background geochemical conditions. The contents of trace elements (except Hg and As) were dominantly controlled by the presence of Fe and Mn oxides as well as by the grain size and the geochemical composition of the sediment. The studied alluvial sediments were not heavily contaminated; there were only few sites where an anthropogenic influence on the concentrations of some metals (Cu, Cd, Zn, and Pb) was noticed. The results from this study show that impact of Pan?evo industrial zone on the quality of the Danube River and its contamination with trace element is minor.     

Migration of As, Hg, Pb, and Zn in arroyo sediments from a semiarid coastal system influenced by the abandoned gold mining district at El Triunfo, Baja California Sur, Mexico

Extensive waste deposits (tailings) and ash from the ignition oven of the abandoned gold mine of mining district El Triunfo (MD-ET) in Baja California Sur, Mexico have released trace elements into the sediments of the Hondo-Las Gallinas-El Carrizal arroyo, which connects to the Pacific Ocean through an evaporitic basin. Migration of these elements through the arroyo is mainly caused by winds or tropical hurricanes that occur sporadically during the summer and cause the otherwise dry arroyo to overflow. To evaluate the concentration and distribution of the elements As, Hg, Pb, and Zn along the 48 km arroyo, surface sediments were collected from 26 sites, ranging from close to the MD-ET to the mouth of the arroyo at the Pacific Ocean. Concentrations in tailings and ash were for As 8890 and 505?000 mg kg(-1); for Hg 0.336 and 54.9 mg kg(-1); for Pb 92,700 and 19,300 mg kg(-1); and for Zn 49,600 and 1380 mg kg(-1). The average of the Normalized Enrichment Factor (Av-NEF) in surface sediments, calculated using background levels, indicates that the sediments are severely contaminated with As and Zn (Av-NEF = 22), Pb (Av-NEF = 24) and with a moderate contamination of Hg (Av-NEF = 7.5). The anthropogenic influence of those elements is reflected in the arroyo sediments as far as 18 km away from the MD-ET, whereas the samples closest to the discharge into the Pacific Ocean show a natural to moderate enrichment for As and Zn and low or no enrichment for Hg and Pb. A principal components analysis identified four principal components that explained 90% of the total variance. Factor 1 was characterized by a high positive contribution of the anthropogenic source elements, especially As, Pb, and Zn (37%), whereas Factor 2 was strongly correlated with the oxy-hydroxides of Fe and Mn (27%). Factor 3 was correlated with Li (16%) and Factor 4 with Al (10%), which indicates more than one source of lithogenic composition, though they played a minor role in the distribution of the elements.     

Metals in water, sediments, and biota of an offshore oil exploration area in the Potiguar Basin, Northeastern Brazil

Metal concentrations were evaluated in water, bottom sediments, and biota in four field campaigns from 2002 to 2004 in the Potiguar Basin, northeastern Brazil, where offshore oil exploration occurs. Analyses were performed by inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Total metal concentrations in water (dissolved?+?particulate) and sediments were in the range expected for coastal and oceanic areas. Abnormally high concentrations in waters were only found for Ba (80 μg?l^?1) and Mn (12 μg?l^?1) at the releasing point of one of the outfalls, and for the other metals, concentrations in water were found in stations closer to shore, suggesting continental inputs. In bottom sediments, only Fe and Mn showed abnormal concentrations closer to the effluent releasing point. Metal spatial distribution in shelf sediments showed the influence of the silt–clay fraction distribution, with deeper stations at the edge of the continental shelf, which are much richer in silt–clay fraction showing higher concentrations than shallower sediments typically dominated by carbonates. Metal concentrations in estuarine (mollusks and crustaceans) and marine (fish) organisms showed highest concentrations in oysters (Crassostrea rhizophorae). Fish tissues metal concentrations were similar between the continental shelf influenced by the oil exploration area and a control site. The results were within the range of concentrations reported for pristine environments without metals contamination. The global results suggest small, if any, alteration in metal concentrations due to the oil exploration activity in the Potiguar Basin. For monitoring purposes, the continental inputs and the distribution of the clay–silt fraction need to be taken into consideration for interpreting environmental monitoring results.     

Metal Fractionation Studies in Surfacial and Core Sediments in the Achankovil River Basin in India

The Fractionation of Fe, Zn, Cu, Pb, Mn and Cd in the sediments of the Achankovil River, Western Ghats, India using a sequential extraction method was carried out to understand the metal availability in the basin for biotic and abiotic activities. Spatial distribution of heavy metals has been studied. Sediment grain size has significant control over the heavy metal distribution. The fluctuations in their concentration partly depend upon the lithology of the river basin and partly the anthropogenic activities. The sediments are dominated by sand and are moderately to strongly positively skewed and are very leptokurtotic in nature. The quartzite and feldspars are abundant minerals along with significant amount of mica with low clay content. The core sediments show increasing trend of heavy metal concentration with depth due to the recent addition of anthropogenic sources and post-diagenic activities. Significant amount of Cd (18%) was found in carbonate fraction, which may pose environmental problems due to its toxic nature. Small concentrations of metals, except Cd and Cu, are in exchangeable fraction, which indicate low bio-availability. Enrichment Factor (EF) for individual metals shows the contribution from terrregious and in part from anthropogenic sources. Selective Sequential Extraction (SSE) study shows the variation in specific metal distribution pattern, their distribution in different phases and their bio-availability. Maximum amount of the metals were bound to the non-residual fractions (mainly Fe-oxides). Overall, bio-availability of these micronutrients from sediments seems to be very less. Non-residual phase is the most important phase for majority of heavy metals studied. Among the non-residual fraction, maximum amount of the heavy metals bound to Fe-oxides. The study high lights the need for in-depth study of heavy metals distribution and fractionation in the smaller river basins to get precise information on the behavior and transport of heavy metals in the fluvial environment and their contribution to the world ocean.     

Dynamics and quantification of dissolved heavy metals in the Mahanadi river estuarine system,India

Dynamics of heavy metals such as Fe, Mn, Zn, Cr, Cu, Co, Ni, Pb, and Cd in surface water of Mahanadi River estuarine systems were studied taking 31 different stations and three different seasons. This study demonstrates that the elemental concentrations are extremely variable and most of them are higher than the World river average. Among the heavy metals, iron is present at highest concentration while cadmium is at the least. The spatial pattern of heavy metals suggests that their anthropogenic sources are possibly from two major fertilizer plants and municipal sewage from three major towns as well as agricultural runoff. The temporal variations for metals like Fe, Cu, and Pb exhibit higher values during the monsoon season, which are related to agricultural runoff. Concentrations of Ni, Pb, and Cd exceed the maximum permissible limits of surface water quality in some polluted stations and pose health risks. Dissolved heavy metals like Fe, Mn, Cr, Ni, and Pb exhibit a non-conservative behavior during estuarine mixing, while Zn, Cu, and Co distribution is conservative. Distribution of cadmium in the estuarine region indicates some mobilization which may be due to desorption. The enrichment ratio data suggest that various industrial wastes and municipal wastes contribute most of the dissolved metals in the Mahanadi River. The Mahanadi River transports 18.216 × 10³ t of total heavy metals into the Bay of Bengal and the calculated rate of erosion in the basin is 128.645 kg km^− 2 year^− 1.     

Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.     

Evaluating the efficiency of sediment metal pollution indices in interpreting the pollution of Haraz River sediments, southern Caspian Sea basin

The Haraz River is one of the most significant rivers in the southern Caspian Sea basin. Towards the estuary, the river receives discharges of industrial, agricultural, and urban wastes. In the present investigation, bulk concentrations of Cu, Zn, As, Cd, Pb, Fe, Ni, Cr, Co, and Sr in Haraz River (Iran) bed sediments were measured from several sample locations. In addition, association of studied metals with various sedimentary phases was assessed to determine the proportions of metals in different forms. The intensity of sediment contamination was evaluated using an enrichment factor (EF), geo-accumulation index (I_geo), and a newly developed pollution index (I_poll). Both EF and I_geo formulae compare present concentrations of metals to their background levels in crust and shale, respectively. In a specific area with its own geological background like Haraz River water basin where naturally high concentrations of metals may be found, such a comparison may lead to biased conclusions regarding levels of anthropogenic contamination. Accordingly, chemical partitioning results are substituted for the mean crust and shale levels in the new index (I_poll). The Pearson correlation coefficient between the anthropogenic portion of metallic pollution in Haraz river-bed sediments with I_poll showed much more value in comparison with those of geochemical accumulation index and enrichment factor. The order of metals introduced by anthropogenic activities are as follows: Sr > Pb > Co > Cd > Zn > Cu > Ni > As > Cr > Fe. The results showed relatively higher concentrations of Cd, As, Sr, and Pb in comparison with those of shale. However, based on the chemical partitioning of metals, it is found that Sr, Pb, Co, and Cd are the most mobile metals. In spite of the high As concentrations in sediments, it is not likely that this element is a major hazard for the aquatic environment since it is found mainly in the residual fraction. Also, Fe, Cr, and Ni are present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments.     

长江下游沉积物中重金属污染现状与特征

对长江下游沉积物中的重金属Co、Cr、Cu、Ni、Pb、Zn、Mn、Hg和As进行全量和醋酸提取态(包括水溶态、可交换态和碳酸盐结合态)分析.结果表明,大部分重金属主要来源于地壳元素的自然释放,但Cu、Zn、Hg和As在最近十几年因受到人为排放的影响质量比有所增加.长江江苏段的重金属质量比普遍高于入海口上海段;位于悬浮物易沉降地区的靖江重金属质量比明显偏高.Cu和Zn总体质量比较高,且醋酸提取态所占比例较大,对长江下游存在潜在的生态风险.     

Dynamics of the lakes in the middle and lower reaches of the Yangtze River basin, China, since late nineteenth century

The middle and lower reaches of the Yangtze River basin have the most representative and largest concentration of freshwater lakes in China. However, the size and number of these lakes have changed considerably over the past century due to the natural and anthropogenic impact. The lakes, larger than 10 km² in size, were chosen from relief maps and remotely sensed images in 1875, 1950, 1970, 1990, 2000, and 2008 to study the dynamics of lakes in the middle and lower reaches of the Yangtze River basin and to examine the causes and consequences of these changes. Results indicated that there was a dramatic reduction in lake areas, which decreased by 7,841.2 km² (42.64 %) during the study period (1875–2008), and the number of lakes in this region changed moderately. Meanwhile, a large number of lakes in the middle and lower reaches of the Yangtze River basin were directly converted into paddy fields, ponds, building lands, or other land-use types over the study period. Therefore, all kinds of lake reclamation should be identified as the major driving factors for the loss of lake in this region. Furthermore, flooding, soil erosion, and sedimentation were also the main factors which triggered lake changes in different periods. Some wetland conservation and restoration projects have been implemented since the 1970s, but they have not reversed the lake degradation. These findings were of great importance to managers involved in making policy for the conservation of lake ecosystems and the utilization of lake resources.     

Heavy metal in surface sediments of the Liaodong Bay, Bohai Sea: distribution, contamination, and sources

In an effort to assess the potential contamination and determine the environmental risks associated with heavy metals, the surface sediments in Liaodong Bay, northeast China, were systematically sampled and analyzed for the concentrations of Cu, Pb, Zn, Cr, Ni, As, and Hg. The metal enrichment factor (EF) and geoaccumulation index (I _geo) were calculated to assess the anthropogenic contamination in the region. Results showed that heavy metal concentrations in the sediments generally met the criteria of China Marine Sediment Quality (GB18668-2002); however, both EF and I _geo values suggested the elevation of Pb concentration in the region. Based on the effect-range classification (TEL-PEL SQGs), Cu, Pb, Ni, and As were likely to pose environment risks, and the toxic units decreased in the order: Ni?>?Pb?>?Cr?>?Zn?>?As?>?Cu?>?Hg. The spatial distribution of ecotoxicological index (mean-ERM-quotient) suggested that most of the surface sediments were “low–medium” priority zone. Multivariate analysis indicated that the sources of Cr, Ni, Zn, Cu, and Hg resulted primarily from parent rocks, and Pb or As were mainly attributed to anthropogenic sources. The results of this study would provide a useful aid for sustainable marine management in the region.     

Origination and assessment of metal pollution in Qarechay River bed sediments

In the present investigation, bulk and chemical partitioning of elements (Cu, Mn, Ni, Zn, Fe, Ca) together with organic matter as a loss in ignition in the Qarechay River bed sediments have been studied. The concentration of metals in Qarechay River bed sediments is governed by the geological units of the study area. The study of anthropogenic portion shows that a small proportion of elemental concentration belongs to this phase. However, Mn has a large portion of anthropogenic sources (43 %). Also, Mn has a share of 13.6 % in sulfide fractions. This result indicates that Mn is a highly mobile element and can easily enter the water column. The presence of Mn in sulfide fraction might be indicative of initial stages of conversion of oxidation state into reduction in Qarechay River. Share of metals in anthropogenic portion is in the following order: Mn (43 %)?>?Cu (19 %)?>?Zn (10 %)?>?Ni (3 %)?>?Fe (0 %). Organic metallic bonds are not significantly present in the study area. Geochemical index (I _geo), pollution index (I _poll), enrichment factor (EF), and pollution load index (PLI) values are indicative of a clean environment throughout the river course. These values are in well agreement with results of chemical partitioning data. Eventually, based on the results of chemical partitioning, regional standard of elements for Qarechay River bed sediments has been established.     

Distribution coefficients (K d) of stable iodine in estuarine and coastal regions, Japan, and their relationship to salinity and organic carbon in sediments

The sediment–water distribution coefficient, K _d, is one of the most important parameters in radionuclide assessment models. In this study, we determined K _ds of stable iodine (I) in estuarine and coastal regions. We studied 16 estuarine and coastal regions of Japan and obtained I data on water and sediments. Data on salinity, pH, dissolved organic carbon and dissolved oxygen in water, and organic carbon (OC) in sediments were also obtained as estuarine variables. Determined K _ds of I in the Sagami River estuary decreased along the salinity gradient (salinity range, 0.1–33.8), indicating that salinity is one of the important factors controlling the K _d values; however, when the K _d values were compared among all the estuaries, the difference between minimum and maximum K _d values varied by about two orders of magnitude in a narrow salinity range of 30.0–34.4. A significant correlation between K _d value and OC content in sediments was observed in all the stations with a salinity of ≥30 except for stations in the Ishikari and Onga River estuaries. The exceptions are probably due to different sources of the sediments, which are explained by the results of relatively low I/OC ratios in sediments in those two estuaries, compared to the other estuaries. Thus, OC in sediments as well as salinity may be responsible for the variation of K _ds of I in the estuarine and coastal regions.     

Assessment of dam removal from geochemical examination of Kuma River sediment,Kyushu, Japan

The aim of this study was to determine if Arase dam gate removal and flushing elevated concentrations of any trace elements in Kuma River and Yatsushiro Bay sediments or caused riverine environmental change. The Arase dam gate on the Kuma River was opened in April 2010. Surface and bottom sediments were compared using 10-cm-long cores (2011) and two grain size fractions. Surface sediment data from 2002, 2012, and 2013 from the Kuma River and Yatsushiro Bay were also compared. The sediments were analyzed using XRF for 23 elements, and the grain size analysis was done. The short core surface and bottom sediments do not show major chemical changes, and therefore, may not represent post-and pre-dam sediments. Results based on 2011 samples show that the removal of the Arase dam gates in 2010 has been geoenvironmentally beneficial due to the decrease of environmentally related trace elements Pb and Zn in 2013. However, a slight increase in the levels of Cr, Cu, Zr, and Nb in 2013 indicates that periodic flushing in winter leads to elevation in these elements due to an increase in the fine fraction. Metal enrichment factors (EF) in 2002 are higher and these have decreased by 2013. Some elements exceed environmental guidelines, but this is due to natural background values, and there is no anthropogenic contamination. Thus, the environment of the river and bay has been significantly improved due to the dam opening. This result suggests that assessment and environmental monitoring studies are very important for dam management and future decision making.     

Evaluation of metal contamination in sediments from north of Morocco: geochemical and statistical approaches

Concentrations of Fe, Mn, Cr, Cu, Ni, Pb, Zn, Cd and Hg were evaluated in surface sediments of two rivers from north of Morocco, known as Souani and Mghogha rivers. Significantly higher concentrations in mg kg^???1 dry weight (dw) of Mn (747.6 vs. 392.9), Cr (86.4 vs. 56.3), Zn (299.5 vs. 138.5) were found in sediment samples from Mghogha when compared with Souani river. Average concentrations of Cd and Hg in several sediment samples from both rivers were above the effect range median that predicts toxic effects to aquatic organisms. The calculation of enrichment factors showed that Mn, Cr, Cu and Ni were depleted, whereas Pb and Hg were enriched. The results of geoaccumulation index revealed that sediments of both rivers were unpolluted with most of the metals and moderately contaminated with Fe and Hg. Some of elevated concentrations of Hg, principally in Mghogha River, were due to anthropogenic sources including the direct discharges of industrial zone.     

Characterization of land-based sources of pollution in Jobos Bay,Puerto Rico: status of heavy metal concentration in bed sediment

As part of an assessment of land-based sources of pollution in Jobos Bay, Puerto Rico, sediment samples were collected at 43 sites to characterize concentrations of a suite of pollutants, including metals. Fifteen major and trace metals (Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn Ni, Pb, Sb, Se, Sn, and Zn) were measured along with total organic carbon and grain size in surficial sediments. For most metals, maximum concentrations were seen in the eastern bay; however, values were still within concentration ranges found in other estuarine systems. In contrast, silver was higher in the western region. In general, metal distribution in the bay was positively correlated with grain size. Additionally, correlations between Al and other metals suggest natural sources for metals. The data presented here suggest that, although the Jobos Bay watershed contains both urban centers along with industrial and agricultural developments, anthropogenic inputs of metals may be negligible.     

Speciation and quantification of Hg in sediments contaminated by artisanal gold mining in the Gualaxo do Norte River,Minas Gerais,SE, Brazil

The Iron Quadrangle in SE Brazil was, in the eighteenth century, one of the most important Au producing regions of Brazil. In this region, gold is produced, even today, by artisanal methods that use Hg to increase the extraction efficiency with no control of Hg release to water systems and the atmosphere. In this context, the Gualaxo do Norte River is of particular interest; its springs are located in the Doce River basin, an important Brazilian basin that supplies water for 3.5 million people. The main goal of this work was to quantify and speciate the Hg in the sediments of the Gualaxo do Norte River using a direct mercury analyzer and gas chromatography-pyrolysis-atomic fluorescence detection system. Statistical analyses consisted of principal component analysis, aiming to assess interactions among elements and species and to group the variables in factors affecting the properties of sediment. The results show that total Hg (THg) and methylmercury (CH₃Hg⁺) concentrations in samples ranged from 209 to 1207 μg kg^?1 and from 0.07 to 1.00 μg kg^?1, respectively (methylation percentages from 0.01 to 0.27%). Thermal desorption analysis showed that mercury is mainly present in the oxidized form, and correlation analyses pointed to a relationship between THg and MnO, indicating that manganese can oxidize and/or adsorb Hg. Together, MO and CH₃Hg⁺ are important parameters in the third principal component, indicating the influence of OM on the methylation process. This first investigation on Hg methylation in this small-scale gold mining area points to the possibility of Hg bioaccumulation and to the need of better understanding the biogeochemical cycle of Hg in this area. Samples were collected in 2012, prior to the 2015 Fundão Dam disaster. The results are also a record of the characteristics of the sediment prior to that event.