Heavy metal pollution in urban topsoils: mineralogical analyses and magnetic characterization

Urban soil samples collected from the city of Xuzhou were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for Pb and Zn. The samples were also investigated for mineralogy using X-ray diffraction, thermal analyses and scanning electron microscopy (SEM). The identified minerals are mainly composed of quartz and calcite as major minerals. Soil samples contained elevated Zn (2,049 ± 5,439 mg/kg) and Pb (115 ± 58 mg/kg). According to the index of geoaccumulation, the soils of the study area are considered to be moderately to strongly contaminated with respect to Zn, moderately contaminated with respect to Pb. The magnetic measurements indicate that the dominant magnetic components are multidomain grains of ferrimagnetic minerals and that superparamagnetic and stable single-domain ferrimagnetic grains and non-ferrimagnetic minerals are present in small magnetic concentrations in this area. The measured metals correlated positively with the determined magnetic parameters (χ, χ _ARM, SIRM and SOFT). This result suggests that simple, rapid, and non-destructive magnetic measurements could provide useful information about Pb and Zn pollution in Xuzhou urban surface soils.     

Heavy metal geochemistry and mineral magnetic characterization of urban soil in Xuzhou,China

In the present study, the enrichment, availability, speciation of heavy metals including Pb, Zn, Cu, Cd, Ni and Sb and magnetic properties of urban soils of Xuzhou (China) were investigated. All analyzed metals showed elevated concentrations compared to local background concentrations. Cadmium and Sb are the metals most enriched in the analyzed area, presenting enrichment factor, on average, of 16.5 and 8.3, respectively. By self-organizing map in combination with diagnostic ratios, the source of Sb, Cd, Cu and Pb in soils might be mainly from traffic emissions. Sequential extractions indicate that metals were primarily associated with the reducible fraction with the exception of Ni. The order of extraction efficiency of various metals was SBET (simplified physiologically based extraction test) > DTPA (diethylenetriaminepentaacetic acid) > CaCl₂. The magnetic results show that soil samples were dominated by a strong ferrimagnetic mineral component with multi- and single-domain magnetic grains. Only CaCl₂ extractable Sb was found to show significant correlations with χlf and SIRM. For both DTPA and SBET extractions, all metals investigated showed significant associations with both χlf and SIRM (saturation isothermal remanent magnetization).     

Environmental magnetic and geochemical characteristics of Chennai coastal sediments,Bay of Bengal,India

In this study, environmental magnetic, heavy metal and statistical analyses were conducted on 21 surface sediments collected from Chennai coast, India, to examine the feasibility of heavy metal pollution using magnetic susceptibility. The Chennai coastal sediment samples are dominated by ferrimagnetic minerals corresponding to magnetite-like minerals. The percentage of frequency dependent magnetic susceptibility reflects the presence of super-paramagnetic/single domain magnetic minerals in Chennai harbour, Cooum and Adayar rivers sediments. High pollution load index in sample E1, E2, CH7, C11, C12 and A16 is mainly due to anthropogenic activities such as, harbour activities, Cooum and Adayar rivers input and industrial effluent. Factor analysis shows that the magnetic concentration dependent parameters (χ, χ _ARM and SIRM) covary with the heavy metal concentrations, suggesting that the input of magnetic minerals and heavy metals in Chennai coastal sediments are derived from the same anthropogenic sources. Strong correlation obtained between pollution load index (PLI) and concentration dependent parameters (χ, χ _ARM and SIRM) for the polluted samples with magnetic susceptibility excess of 50×10^− 8 m³kg^− 1. Significant correlations between heavy metals and magnetic susceptibility point out the potential of magnetic screening/monitoring for simple and rapid proxy indicator of heavy metal pollution in marine sediments.     

Mobilisation of traffic-derived trace metals from road corridors into coastal stream and estuarine sediments,Cairns, northern Australia

This investigation revealed the presence of traffic-derived metals within road, stream and estuarine sediments collected from a coastal catchment, northern Australia. Studied road sediments displayed variable total metal concentrations (median Cd, Cu, Pb, Pd, Pt, Ni and Zn values: 0.19, 42.6, 67.5, 0.064, 0.104, 36.7 and 698 mg/kg, respectively). The distinctly elevated Zn values are due to abundant tyre rubber shreds (as verified by SEM-EDS and correlation analysis). By comparison to the road sediments, background stream sediments taken upstream from roads have relatively low median Pb, Pd, Pt and Zn concentrations (7.3 mg/kg Pb, 0.01 mg/kg Pd, 0.012 mg/kg Pt, 62 mg/kg Zn). Stream and estuarine sediment samples collected below roads have median values of 21.8 mg/kg Pb, 0.014 mg/kg Pd, 0.021 mg/kg Pt and 71 mg/kg Zn, and exhibit ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios that appear on a mixing line between the isotopically distinct background stream sediments and the road sediments. Thus, mobilisation of dusts and sediments from road surfaces has resulted in relatively elevated Pb, Pd, Pt and Zn concentrations and non-radiogenic Pb isotope ratios in local coastal stream and estuarine sediments. The investigation demonstrates that traffic-derived metals enter coastal stream and estuary sediments at the fringe of the Great Barrier Reef lagoon.     

Metal geochemical and mineral magnetic characterization of the <2.5 μm fraction of urban soils in Xuzhou (China)

The concentrations of metals (Pb, Cu, Zn, Co, Ni, Fe and Mn) in the <2.5 μm fraction of surface soils (0–5 cm) from highly industrialized areas in Xuzhou (China) were determined. All analyzed metals with the exception of Mn and Co in the present study showed elevated concentrations in the <2.5 μm fraction of soils compared to background concentrations, particularly for Zn. Metal enrichment was positively correlated with carbonate complexation constants (but not bulk solubility products) as well as the first stability constants of metal-citrate, likely suggesting that both metal–organic complexation and/or precipitation of carbonate surfaces that subsequently adsorb metals are likely responsible for these metal enrichment on these samples. Sequential extraction analysis shows the metals Pb, Cu, Zn, Co and Mn were largely associated with the reducible fraction, whereas Ni was largely associated with the oxidisable fraction. Manganese is the only metal showing significant association with the exchangeable fraction (up to 33 %), suggesting that it may be the most susceptible metal to mobilization. Mineral magnetic analysis indicates that ferrimagnetic SSD + SP (stable single domain + superparamagnetic) minerals dominated the <2.5 μm fraction of Xuzhou surface soils. Lead, Cu and Zn were found to show significant correlations with χlf (p < 0.01), suggesting that magnetic technique might be beneficially used as a rapid and inexpensive method to estimate these metal contaminations in the <2.5 μm fraction of surface soils.     

High spatial resolution sampling of metals in the sediment and water column in Port Jefferson Harbor, New York

Eighteen sediment samples and six water-column samples were collected in a small (6 km²), coastal embayment (Port Jefferson Harbor, New York) to define a high-resolution spatial distribution of metals and to elucidate sources of contaminants to the harbor. Sediment metal (Ag, Cu, Fe, Ni, Pb, V, and Zn) concentrations varied widely, reflecting differences in sediment grain size, with higher metal concentrations located in the fine-grained inner harbor sediments. Calculated enrichment factors for these sediments show that Ag, Pb, Cu, and Zn are elevated relative to both crustal abundances and their respective abundances in sediments in central Long Island Sound. Metal concentrations were 1.2 to 10 fold greater in water from the inner harbor compared to water from Long Island Sound collected outside the mouth of the harbor. Spatial variations in trace metals in surface waters within the bay parallel the spatial variations of trace metals in sediments within the harbor. Elevated water-column metal concentrations appear to be partially derived from a combination of diagenetic remobilization from contaminated sediments (e.g., Ag) and anthropogenic sources (e.g., Cu and Zn) within the southern portions of the harbor. Although the National Status and Trends Program had reported previously that sediment metal concentrations in Port Jefferson Harbor were low, the results of this study show sediment metals have high spatial variability and are enriched in the inner harbor sediments at levels comparable to more urbanized western north shore Long Island harbors.     

A comparison of the early diagenetic environment in intertidal sands and muds of the Manukau Harbour,New Zealand

The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS₂ are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO₃, FeCO₃, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS₂, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.     

A palaeomagnetic and mineral magnetic study of the loess sequence at Liujiapo,Xian, China

Employing an average vertical sampling interval of 20 cm, oriented samples were collected from 26 m of the loess section at Liujiapo, near Xian, China in order to refine the existing magnetostratigraphic record. Palaeomagnetic results reveal two short reversed-polarity subzones within a profile of predominantly normally magnetised sediments, an interpretation that is at variance with previous results from this section and from other studies of Chinese loess. Investigation of sediment mineral-magnetic properties indicates a close correspondence between down-section variations in intensity of magnetisation, susceptibility and saturation isothermal Journal of Quaternary Science remanence (SIRM), and lithology. The ratios IRM_-100mT/SIRM and SIRM/ susceptibility appear to be particularly sensitive indicators of the degree of soil development and hence of palaeoclimate.     

Speciation Study of Cr in a Geochemical Reference Material Sediment Series Using Sequential Extraction and XANES Spectroscopy

Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.     

The role of zooplankton fecal pellets in the sedimentation of polycyclic aromatic hydrocarbons in Dabob Bay,Washington

Polycyclic aromatic hydrocarbon (PAH) compositions were determined in plankton, sediment-trap-collected particulate material and sediment cores from Dabob Bay using a high performance liquid Chromatographie (HPLC)/fluorescence technique. The annual flux of individual PAH measured in a series of sediment traps was compared with the flux of corresponding compounds determined from ²¹⁰Pb dated bottom sediments. Systematic seasonal variations in the fluxes and concentrations of PAH, Al and organic carbon in the trap-collected particulates and seasonally collected plankton were also investigated to determine whether or not PAH are associated with either terrestrial or marine-derived materials.Concentrations of all PAH studied increased tenfold within the last 80–100 yr of sediment deposition, except for perylene which displayed a reasonably constant concentration profile. This suggests at least two sources contribute to the observed sedimentary PAH compositions in Dabob Bay, i.e., anthropogenic combustion and a natural source. Plankton and sediment trap-collected particulates contained PAH mixtures qualitatively similar to underlying surface sediments. Microscopic examination indicated fecal pellets were the major form of particulate material in the sediment traps. The fecal pellets collected in the sediment trap time series quantitatively account for essentially 100% of the PAH fluxes measured in the ²¹⁰Pb dated sediments, implying Zooplankton fecal pellets control the removal of PAH to Dabob Bay sediments. These measurements provide clear evidence that the PAH studied are not produced after sediment deposition. The observed seasonal covariations of PAH and Al in both sediment trap and plankton samples further indicate that PAH originate from terrestrially-based sources, are introduced into the marine environment by runoff and erosion or atmospheric deposition and are not produced by marine plankton.     

潮滩表层沉积物磁性特征的季节性变化及其对沉积动力作用的响应:以杭州湾北岸为例

根据2004年9月—2005年8月杭州湾北岸中潮滩固定观测点重复采集的表层沉积物的磁学参数和粒度分析,探讨了研究区域潮滩沉积物磁学性质的季节性变化及其对沉积动力的响应。 结果表明, 该观测点潮滩沉积物磁学参数存在显著的月际变化,2004年12月底—2005年5月上旬的半年中,SIRM、χARM、χfd%、χARM/χ、χARM/SIRM等参数出现高值,指示了沉积物中含有较多的细晶粒亚铁磁性矿物,对应于潮滩淤积时段和较细的沉积物粒级组成,其余各月上述磁参数值较低,对应于潮滩沉积物较粗的侵蚀期。上述结果表明,沉积物的磁性特征可以很好地反映潮滩冲淤过程中沉积动力的变化。     

Sediment pollution in the Vågen,Bergen harbour,Norway

Recent sediments in the Vågen, Bergen harbour, are subjected to injection of untreated sewage from around 15,000 person equivalent. Here the distribution of trace elements is mapped in surface and subsurface sediments. Selected trace-element concentrations decrease from the inner towards the outer Vågen. These concentration gradients do not correlate with minerogenic grain size. Linear correlation, combined with enriched sediment trace elements, are used to infer sources for these elements and possible reasons for their enrichment. (1) Frequent use of dental amalgam might be related to the enrichments of and correlation between Ag, Cu, Hg and Sn in surficial sediments pre-1994. (2) Enrichment and correlation of Cu/Zn may be related to the commercial and private use of anti-fouling boat-paint. Further, tributyltin is suggested as a source of Sn enrichment. (3) Increased traffic in the city of Bergen with gasoline combustion and car-wheel wear-off release Pb and Zn. (4) Hg and Pb might have been atmospherically supplied due to the combustion of coal in a nearby gas plant pre-1985. (5) No correlation is observed between enriched Vågen trace metals and bedrock element composition of the surrounding mountains, indicating a minor supply from erosion.     

Distribution of Pb between sediments and pore water in Woods Lake,Adirondack State Park,New York,U.S.A.

Interstitial water samples and sediments were collected from acidified Woods Lake (pH= 5.0) to evaluate Pb profile stability and distribution between the solid and aqueous phases. A simple equation was developed to describe the distribution coefficient for Pb(Kd_Pb), based on the sample moisture content and analyte concentrations in bulk sediment and pore water. In Woods Lake sediment Kd_Pb values ranged from 6.7 × 10⁴to6.7 × 10⁵ml/g. The affinity of Pb for the solid phase was further demonstrated by inverting a sediment core and leaving it for 10 months in situ. Upon retrieval, the Pb profile was found to have remained intact over the same depth, albeit inverted, as in the surrounding sediment. Geochemical modeling using MINTEQA2 demonstrates that Pb solids that may reasonably be expected to precipitate were all undersaturated by several orders of magnitude with respect to the interstitial water, indicating that Pb was sorbed to, rather than precipitated in, Woods Lake sediment.     

Heavy metal concentrations in roadside-deposited sediments in Kuwait city

In the present study, roadside-deposited sediment samples collected from Kuwait city district, in Kuwait, were analyzed for specific heavy metals (As, Cr, Cu, Mn, Ni, Pb, and Zn). Contamination assessment status of heavy metals in roadside sediments was made using mathematical models in terms of enrichment factor (EF), geoaccumulation index (I _geo), and contamination factor (CF). The sediments showed remarkably high levels of all the metals, except Ni, above background concentrations in the following order (As, Cu, Pb, Zn, Mn, and Cr). CF and I _geo revealed overall moderately uncontaminated and moderate contamination, respectively, but the EFs for all metals ranged between moderate and significant enrichment.     

大同盆地高砷地下水系统沉积物环境磁学特征

为了研究高砷含水层沉积物中砷与磁性矿物的关系, 对大同盆地高砷地区含水层钻孔样品进行了环境磁学和地球化学分析, 结果表明亚铁磁性矿物是决定含水层沉积物磁性特征的主要磁性矿物.通过对比砷和磁性参数在垂向上的变化趋势发现, 高砷含量往往对应着低的饱和等温剩磁(SIRM) 值, 揭示出砷和顺磁性矿物之间也存在联系.沉积物砷含量与磁性参数的相关系数均小于0.5 (α=0.05), 表明砷和亚铁磁性矿物及不完整反铁磁性矿物之间不存在明显的联系.在所有磁性参数中磁化率(χ)和砷含量之间相关性最显著, 相关系数均在0.4 (α=0.05) 左右, 低的相关系数与亚铁磁性矿物和不完整反铁磁性矿物对顺铁磁性矿物的稀释有关.该地区高砷地下水的形成可能与水铁矿及纤铁矿等砷的赋存矿物在还原条件下的还原溶解有关.      

The influence of particle size variations on the magnetic properties of sediments from the north-eastern Irish Sea

This paper considers the magnetic properties of a range of recent and contemporary sediments from the north eastern part of the Irish Sea. Principal component ordinations of the results show a close link between magnetic property variations and particle size. The magnetic properties of a subset of samples, particles sized by a combination of sieving and pipette analysis, confirm that variations in ferrimagnetic (‘magnetite’) grain size parallel those in particle size, despite the fact that the magnetic grains in the fine grades have diameters 1–2 orders of magnitude smaller than those of the particle size fraction in which they occur. This is best explained by postulating that the fine magnetic grains occur in the clay fraction but are present in declining concentrations in the coarser grades up to 4ø as an artefact of the pipette method. Most samples have a biomodal distribution of magnetic minerals, with a coarse mode associated with heavy minerals in the sands or coarse silts, and a fine mode in the clays. Magnetic susceptibility (x) and saturation isothermal remanent magnetization (SIRM) largely pick out the coarse mode where present; anhysteretic remanent magnetization (ARM) largely picks out the fine mode. The results open up the possibility of normalizing samples from these environments for particle size and, more specifically, clay content, by means of ARM or ARM/x values. The most likely source for the uniform and almost exclusive stable single domain magnetite, which dominates the magnetic properties of the clays, is thought to be bacterial magnetosomes. The measurements as a whole do not appear to hold much promise for discriminating sediment source types.     

Azaarenes in Puget sound sediments

The first quantitative measurements of azaarenes in marine sediments are reported for Puget Sound, in northwestern Washington State, U.S.A. Two- to four-ring azaarenes, in concentrations as low as 50 ppb (relative to organic carbon), are measured in ²¹⁰Pb dated sediments using glass capillary gas chromatography combined with nitrogen-selective detection.Azaarene distributions are geographically and temporally variable. Azaarene distributions in upper sediment layers suggest that total azaarene concentrations are related to proximity to urban areas, and may be anthropogenically derived. Subsurface maxima between 6 and 17 cm in several cores resemble similar maxima in PAH and organo-sulfur compounds. Trace quantities of azaarenes present in sediments, deposited prior to urbanization of the Puget Sound region, suggest low-level natural azaarene sources. One core containing particulate coal produced a concentrated and complex azaarene mixture, suggesting either introduction of mined coal or erosion of regional coal deposits. Analyses of possible azaarene sources indicate that although azaarene compositions vary between sources, coal azaarenes can be distinguished from petroleum azaarenes by their ratios of 2-ring to 3-ring azaarenes, and may identify predominant azaarene inputs in environmental samples. Gross differences in azaarene composition exist between European and American air particulates and sediments, suggesting differences in azaarene sources.     

Extraction of heavy metals in Sydney Harbour sediments using 1M HCl and 0.05M EDTA and implications for sediment‐quality guidelines

Sixty sediment samples with a wide range of heavy‐metal concentrations and sediment textures were collected from Sydney Harbour. The samples were extracted with 1M HCl, 0.05M EDTA and HClO₄/HNO₃ and analysed by flame atomic absorption spectrometry for Zn, Pb, Cu and Cd. 1M HCl extracted a large proportion of heavy metals in oxic sediments (60–100%), whereas the extractability of metals with 0.05M EDTA was generally lower (by ～20%). Extractability was unrelated to the level of contamination or to sediment texture. The extractability of Cu in anoxic sediments was substantially lower with 1M HCl (～20%) and 0.05M EDTA (～10%) than with HClO₄/HNO₃. The extractability of Pb with 0.05M EDTA was also reduced in anoxic sediments (to ～70%). The use of weak extractants, in particular 1M HCl, is recommended by the recently introduced ANZECC and ARMCANZ interim sediment‐quality guidelines. These extractants are believed to provide a better measure of the bioavailable metal content than strong acid extractants. In this study, anoxic, sulfidic environments had a major influence on metal extractability with weak extractants. The implication of this is that the number of samples requiring further testing, as stipulated by the guidelines, would be significantly reduced in anoxic sediments.     

A contemporary contamination record of stormdrain and harbour sediments, Wellington, New Zealand

 Sediments from stormdrain catchments and outlets in Wellington city and sediment traps from Wellington Harbour were sampled for trace metal content. Samples were analysed for total metal content using XRF and ICP-MS. High values of Pb and Zn were found in stormdrain catchments and outlets, decreasing to elevated background rock levels in the harbour. Maximum values were recorded in an inner city stormdrain catchment, with levels of Pb (4605 ppm), Cu (2981 ppm) and Zn (3572 ppm) all higher than the biological probable effects levels (PEL). Concentrations of As, Cr, Cu, Pb, Ni and Zn concentrations in all harbour sediment trap samples were below the PEL. The mean values for each harbour sediment trap sample can be used as an accurate historical baseline in future studies. Stormdrain samples with high trace metal levels were close to industrial and construction sites. The proximity of these outlets to recreational areas should be of concern to local authorities. Received: 28 August 1997 · Accepted: 15 December 1997     

Geochemical fractionation of Ni,Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment

Metal speciation study in combination with major element chemistry of deep sea sediments provided possible metal enrichment pathways in sediments collected from environmentally different locations of Central Indian Ocean Basin (CIB). Metal speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase (within the Fe–Mn oxyhydroxide binding phases) was the major host for all the three metals in the studied sediments. Major element chemistry of these sediments revealed that there was an increased tendency of Cu and Ni to get incorporated into the deep sea sediment via the non-terrigenous Mn-oxyhydroxide fraction, whereas, Pb gets incorporated mostly via amorphous Fe-hydroxides into the sediment from the CIB. This is the first attempt to provide an insight into the mechanism of metal enrichment in sediment that host vast manganese nodule.