Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

Vertical distribution of heavy metals in grain size fractions in sedimentary rocks: Mosina–Krajkowo water well field, Poland

The paper presents the results of heavy metals determination in samples of sedimentary rocks from the Mosina-Krajkowo water well field (Poland). The concentration of heavy metals was analysed by type of rock (sand, gravel, warp, silt, till, and clay). Variation of heavy metal concentrations with depth was studied taking into account the age series of the rocks (fluvial sediments of the modern Warta River valley, sediments of the Baltic Glaciation, tills of the Middle-Polish Glaciation, sediments of the Masovian Interglacial (Holstein), tills of the Poznań series) and granulometric fractions. The grain sizes considered included: >2.0, 2.0-1.0, 1.0-0.5, 0.5-0.25, 0.25-0.1, 0.1-0.063, and <0.063 mm. The concentrations of the heavy metals studied were found to change with the type of rock, age series, and granulometric fraction. The levels of the metals were determined by the technique of atomic absorption spectrometry with flame atomisation (F-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

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.     

Groundwater environmental capacity and its evaluation index

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K_NRF) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K_NRF both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37–99% from the background levels less than 30%.     

Mercury speciation in the Persian Gulf sediments

The concentrations of total mercury (Hg) and methyl mercury (MMHg) were determined in 78 marine sediments in the Iranian coastal waters of the Persian Gulf along nine transects perpendicular to the coastline. Total Hg ranged from 10 to 56 ng g( - 1)d.w. and MMHg from 0.1 to 0.4 ng g( - 1) d.w. The fraction of methyl mercury accounted from 0.3% to 1.1% of the total mercury amount. The organic carbon (OC) content ranged from 0.4% to 1.8%. The present study indicates that the levels of Hg in the sediments of the Iranian coast of the Persian Gulf were all in the concentration range of unpolluted areas regarding Hg (<100 ng g( - 1)). The concentrations of total Hg, methyl mercury and organic carbon were generally higher in the deeper stations. Total Hg and MMHg were significantly correlated, but no significant correlations could be found between the Hg and OC levels.     

Speciation of selected heavy metals geochemistry in surface sediments from Tirumalairajan river estuary, east coast of India

Surface sediment samples from the Tirumalairajan river estuary were studied for grain size pattern, organic matter, and heavy metals (Fe, Mn, Zn, and Pb) using the sequential and bulk metal extraction methods to evaluate metal behavior. Ten surface sediment samples were collected during the monsoon and summer seasons of the year 2009. The observed orders of concentrations of heavy metals in the sediments were as follows: Fe?>?Mn?>?Zn?>?Pb. The results obtained from sequential extraction showed that, among the metals studied, a larger portion of the metals were associated with the residual phase, although they are available in other fractions. The low concentration of metals available in bioavailable phases indicated that the sediments of Tirumalairajan river estuary were relatively unpolluted. Correlation analysis was also carried out to understand the associations of metals in different phases with sand, silt, clay, and organic matter. To understand the risk of heavy metals to sediment-dwelling organisms, the data were compared with risk assessment code and sediment quality values using the screening quick reference table. The main source of metals to the estuary is from the irrigation field and its associated activities in the study area.     

Mercury in the sediments of Vembanad Lake,western coast of India

Mercury, a global pollutant, is popping up in places where it was never expected before and it burdens in sediments and other non-biological materials. It is estimated to have increased up to five times the pre-human level due to anthropogenic activities. Vembanad backwaters, one of the largest Ramsar site in India, which have extraordinary importance for its hydrological function, are now considered as one of the mercury hot spots in India. In this study, surface sediment samples of Vembanad Lake and nearshore areas have been seasonally analysed for total mercury and methyl mercury concentrations while the core sediment samples were analysed for total mercury. The results showed that the northern part of the lake was more contaminated with mercury than the southern part. The mercury concentration was relatively high in the subsurface sediment samples, indicating the possibility of historic industrial mercury deposition. A decreasing trend in the mercury level towards the surface in the core sediment was also observed. The geochemical parameters were also analysed to understand the sediment mercury chemistry. Anoxic conditions, pH and organic carbon, sulphur and Fe determined the presence of various species of mercury in the sediments of Vembanad Lake. The prevailing physical and geochemical conditions in Vembanad Lake have indicated the chances of chemical transformation of mercury and the potential hazard if the deposited mercury fractions are remobilised.     

Spatial variation of potentially toxic elements in different grain size fractions of marine sediments from Gulf of Mannar, India

Marine sediments of the Gulf of Mannar (GoM), India are contaminated by potential toxic elements (PTEs) due to anthropogenic activities posing a risk to the existing fragile coral ecosystem and human health. The current study aimed to assess the distribution of PTEs (arsenic—As; cobalt—Co; copper—Cu, molybdenum—Mo; lead—Pb; and zinc—Zn) in marine sediments of different grain size fractions, viz., medium sand (710 μm), fine sand (250 μm), and clay (<63 μm) among the different coastal regions of Pamban, Palk Bay, and Rameswaram coasts of GoM, using grain size as one of the key factor controlling their concentrations. The concentrations of PTEs were measured in the different size fractions of sediment using inductively coupled plasma mass spectrophotometer. The order of accumulation of all PTEs in the three fractions was ranked as Zn > Cu > Pb > As > Co > Mo and in the three locations as Rameswaram > Palk Bay > Pamban. The concentration of PTEs in Palk Bay and Rameswaram coast was significantly different (P?<?0.05), when compared to Pamban coast. Measured geoaccumulation index (I _geo) and contamination factor (CF) indicated significant enrichment of Co and Pb from Rameswaram coast when compared to other two coasts. Although the concentration of Co was low but the measured I _geo and CF values indicated significant enrichment of this PTE in Rameswaram coast. The increased input of PTEs in the coastal regions of GoM signifies the need to monitor the coast regularly using suitable monitoring tools such as sediments to prevent further damage to the marine ecosystem.     

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.     

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.     

Sequential fractionation of phosphorus in lake sediments of Northern Greece

The amounts and forms of potentially mobile P in surface sediments from two lakes, Volvi and Koronia, located in Northern Greece were evaluated using a sequential chemical extraction. Five sedimentary P reservoirs were separately quantified: loosely sorbed P (NH₄Cl-P); iron associated P (BD-P); calcium bound P (HCl-P); metal oxide bound P (NaOH-P) and residual P (organic and refractory P). Samples were taken in two seasons and the average concentration of the fractions of phosphorus were calculated. The results indicated that the TP content and chemically extractable phosphorus in the sediments of Koronia Lake were higher than those of Volvi Lake. Sediment TP was also strongly and positively correlated with sediment Fe. Fine-sized sediments exhibited significantly higher concentrations for both lakes than the sand fraction. The P in the surface sediment mainly consisted of HCl-P and Res-P, while NH₄Cl-P and BD-P only constituted a minor part. The rank order of the different P extracts was the same for the two lakes and was Residual-P > HCl-P > NaOH-P > BD-P > NH₄Cl-P.     

Total and methyl mercury in the water,sediment, and fishes of Vembanad,a tropical backwater system in India

Mercury contamination in the water bodies of developing countries is a serious concern due to its toxicity, persistence, and bioaccumulation. Vembanad, a tropical backwater lake situated at the southwest coast of India, is the largest Ramsar site in southern India. The lake supports thousands of people directly and indirectly through its resources and ecosystem services. It is highly polluted with toxic pollutants such as heavy metals, as it receives effluent discharges from Kerala’s major industrial zone. In the present study, water, pore water, sediment, and fish samples collected from Vembanad Lake were analysed for total mercury (THg) and methyl mercury (MHg) contents. The maximum concentrations of THg and MHg in surface water samples were31.8 and 0.21 ng/L, respectively, and those in bottom water samples were 206 and 1.22 ng/L, respectively. Maximum concentration of THg in surface sediment was observed during monsoon season (2850 ng/g) followed by that in the pre-monsoon season (2730 ng/g) and the post-monsoon season (2140 ng/g). The highest sediment concentration of MHg (202.02 ng/g) was obtained during monsoon season. The spatial variation in the mercury contamination clearly indicates that the industrial discharge into the Periyar River is a major reason for pollution in the lake. The mercury pollution was found to be much higher in Vembanad Lake than in other wetlands in India. The bioaccumulation was high in carnivorous fishes, followed by benthic carnivores. The THg limit in fish for human consumption (0.5 mg/kg dry wt.) was exceeded for all fish species, except for Glossogobius guiris and Synaptura orientalis. The concentration of THg was five times higher in Megalops cyprinoides and four times higher in Gazza minuta. Significant variation was observed among species with different habits and habitats. Overall, risk assessment factors showed that the mercury levels in the edible fishes of Vembanad Lake can pose serious health impacts to the human population.     

治理后的太湖无锡区域底质中重金属污染现状及生态风险评价

以2005年以后太湖无锡区域底质为研究对象，分析了太湖底泥中重金属的含量分布及富集状况，采用地积累指数法和潜在生态危害指数法对重金属的生态危害进行评价。结果表明：太湖无锡区域底质受重金属轻度污染，含量高于全国水系沉积物平均值；地积累指数法显示太湖无锡区域底质中重金属污染排序为Cu=As〉Pb〉Zn〉Cr〉Cd〉Hg；金属对太湖无锡区域底质构成的潜在生态危害由强到弱为Hg〉Cu〉As〉Cd〉Pb〉Cr〉Zn；从区域上看，2种评价方法均表明底质中重金属危害程度为宜兴沿岸区〉梅梁湖〉五里湖〉贡湖无锡水域。     

Sediment and Suspended Matter Lead Contamination in the Gulf of Kavala, Greece

Sediment and suspended particulate matter samples from 24 stations in the Gulf of Kavala have been examined for lead contamination. Grain size analysis and organic matter content were also performed. Total – anthropogenic sediment lead concentrations and enrichment factors at stations close to harbors and chemical industries were found higher (up to 209–135μg/g and 4.12 respectively), in relation to concentrations from the rest of the coastal zone. In the above areas, increased suspended particulate lead in the bottom of the water column was also recorded (up to 109μg/g). Total sediment lead concentrations composed of high natural Pb background increased with decreasing grain size, suggesting their association with the fine fractions of the sediments (31.1–66.0% mud presence) and the organic matter content (6–9% higher values). Overall, higher total lead concentrations in the sediments, determined by this work, appear to be significantly different from those reported for the Gulf of Kavala in previous studies and similar to those detected in other highly contaminated eastern Mediterranean coastal areas.     

Mercury in chemical fractions of recent pelagic sediments of the sea of Japan

The distribution of mercury (Hg) in chemical fractions (H2O, 0.05 M Na2-EDTA pH 3, 1 M HCl, humic and fulvic acids, and non-hydrolysing residue) of recent pelagic sediment cores of the Sea of Japan (East Sea) was studied. Total Hg content in the sediments was rather low: 83 +/- 30 (21-173) etag g(-1), indicating the absence of substantial specific sources of the element in the deep part of the sea. Hg content within the sediment core varied by a factor of 1.3-1.8, showing peaks that coincide with the near-surface and buried sediment slices of light brown and brown "oxidized" colours and evidencing Hg redox-sensitive diagenetic redistribution. Hg exerted its maximum mobility in the near-surface sediment strata as a component of water-soluble organic matter. Despite the predominance of fulvic acids in extracted humus fractions, humic acids were a much more efficient concentrator for Hg (0-79 vs. 188-233 microg Hg g(-1) C(org), respectively). Nevertheless, the most refractory non-hydrolyzing residue (humin) fraction contained the principal Hg pool in the sediments. Hg content in all the extracted fractions decreased with core depth, thus indicating Hg immobilization as a principal tendency in Hg fate during post-depositional diagenesis.     

The Contamination Levels of Organochlorine Pesticides in Water and Sediment Samples in Uluabat Lake, Turkey

The Uluabat Lake is a reservoir of 125 km² surface area, in the boundaries of Bursa province, Turkey. The results showed that Uluabat Lake was still contaminated by organochlorine pesticides and their residues despite the existence of bans over a long time. Considerable amounts of organochlorine pesticides (HCB, p.p^′-DDT, p.p^′- DDE, α -, β- and γ-BHC, Aldrin, Heptachlor epoxide, Endrin, Endosulfan I and II) were detected in water and sediment samples during one-year study in this lake. Samples of water and sediment were collected in different regions, (6 sampling point) of the lake between February 2002 and November 2002.The mean levels of organochlorine pesticides in water and sediments were determined. According to results, it was found that various environs in Uluabat Lake were contaminated by 11 different organochlorine pesticides. Residue analyses showed that higher organochlorine pesticides and their residues were generally more accumulated in the sediment samples.     

The success of elutriate tests in extended prediction of water quality after a dredging operation under freshwater and saline conditions

Dredging simulation by elutriate tests accurately predicted concentrations of Hg, Cu, Mn and Fe released to the water column from contaminated sediment to within 1 order of magnitude. Hg and Cu concentrations increased by up to 7-fold after dredging, but declined to background concentrations within 48 h. Maximum loadings of Hg and Cu coincided with Fe and total organic carbon (TOC) water column concentrations, suggesting Hg and Cu are adsorbed onto particulates of Fe oxides and organic material. Seasonal changes in redox potential and temperature did not significantly affect metal release from sediments. Saline water did not cause significant increases in contaminant release from sediments to the water column over that observed for freshwater. Water quality standards of 1 µg l^–1 Hg and 28 µg l^–1 Cu as annual averages were not breached by dredging operations. Long-term effects of dredging on Hg and Cu availability, due to deposition of contaminated material as surficial sediments, is, however, of concern.     

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.     

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.