Geogenic Metals Research Articles

Profile Distributions of Potentially Toxic Metal(loid)s in Soils of the Middle Odra Floodplain (SW Poland).

Floodplain soils are often contaminated with potentially toxic elements of geogenic and anthropogenic origin. This also applies to a valley of the Odra river, which in its upper reach flows through areas of historical and contemporary mining and heavy industry. This study examined the distribution of typically anthropogenic metal(loid)s, i.e., Pb, Zn, Cu, As and Cd, and geogenic metals, i.e., Mn and Fe, in soil profiles of the middle Odra valley, and analyzed factors that determine their concentrations. Thirteen soil profiles, located inter the embankment area and outside the embankments, were examined. Most of profiles indicated stratification typical for alluvial soils. Topsoil layers in the inter-embankment zone showed considerable enrichment in Pb, Zn and Cd, and to a lesser extent in Cu and As. Low soil pH is an important factor of environmental risk; therefore, acidic soils definitely require liming. The soils located out of embankments did not show any considerable enrichment in the elements examined. Based on significant correlations between the concentrations of metal(loid)s in deep soil layers and soil texture, the values of local geochemical background were derived. Outliers, particularly in the case of As, were explained by possible redistribution under reducing conditions.

Complex patterns of phosphorus delivery in the Lake of the Woods watershed

Lake of the Woods (LoW) is a large, transboundary lake that continues to experience harmful algal blooms despite large declines in phosphorus (P) inputs from point sources. Tributary runoff is considered the largest source of P to the lake; however, there are few monitoring data within the Canadian portion of the basin (∼60% of total area), to guide management. To address this gap, we monitored five rivers of contrasting land use within the lower Rainy River region, an acknowledged “hot spot” of P delivery in the basin. Total P (TP) concentrations were consistently high at all five rivers (volume-weighted range: 19–215 μg/l) despite differences in agriculture across sites (7–27%), suggesting ‘natural’ background P levels are high in this landscape. Furthermore, TP concentrations were strongly correlated with total suspended sediment and geogenic metals, iron (Fe) and aluminum, and TP was especially high during events (>400 μg/l) indicating erosion is an important source of P delivery. However, equally high TP and Fe during periods of slow, stagnant flow in the summer and under winter ice suggest erosion is not the only source of P. Instead, we suggest redox release of P from streambed sediment is also important. This observation is significant, because internal P release within the tributaries, especially during the summer could ‘seed’ downstream algal blooms. The strong sensitivity of TP to both high and low flow conditions indicates that frequent, all-season, multi-year measurements are needed to understand the mechanisms of P delivery in this basin.

Recognition of the importance of geogenic sources in the content of metals in PM2.5 collected in the Mexico City Metropolitan Area.

The study of airborne metals in urban areas is relevant due to their toxic effects on human health and organisms. In this study, we analyzed metals including rare earth elements (REE) in particles smaller than 2.5μm (PM2.5), collected at five sites around the Mexico City Metropolitan Area (MCMA), during three periods in 2011: April (dry-warm season, DW), August (rainy season, R), and November (dry-cold season, DC). Principal component analysis allowed identifying factors related to geogenic sources and factors related to anthropogenic sources. The recognition of the high impact of geogenic sources in PM2.5 is in agreement with the REE distribution patterns, which show similar behavior as those shown by igneous rocks, confirming the influence of the regional geogenic material. Metals associated to geogenic sources showed higher concentration (p < 0.05) at NE of the MCMA and a significant correlation with prevalent winds. Geogenic metals show similar seasonal distribution, with the highest concentration during DW (p < 0.05), suggesting a possible metal resuspension effect which affects more significantly at lower relative humidity (RH). The metals associated with anthropogenic sources are in agreement with the urban complexity of the area, showing homogenous distribution throughout MCMA (p > 0.05) and no similar seasonal pattern among them. These unexpected results exposed outstanding information regarding the identification of different geogenic sources as the main contributors of metals in the atmospheric environment in the MCMA and highlighted the importance of meteorology in the spatial and seasonal metal patterns.

Analysis of some metallic elements and metalloids composition and relationships in parasol mushroom Macrolepiota procera

The aim of the study was to characterise the multi-elemental composition and associations between a group of 32 elements and 16 rare earth elements collected by mycelium from growing substrates and accumulated in fruiting bodies of Macrolepiota procera from 16 sites from the lowland areas of Poland. The elements were quantified by inductively coupled plasma quadrupole mass spectrometry using validated method. The correlation matrix obtained from a possible 48 × 16 data matrix has been used to examine if any association exits between 48 elements in mushrooms foraged from 16 sampling localizations by multivariate approach using principal component (PC) analysis. The model could explain up to 93% variability by eight factors for which an eigenvalue value was ≥1. Absolute values of the correlation coefficient were above 0.72 (significance at p < 0.05) for 43 elements. From a point of view by consumer, the absolute content of Cd, Hg, Pb in caps of M. procera collected from background (unpolluted) areas could be considered elevated while sporadic/occasional ingestion of this mushroom is considered safe. The multivariate functional analysis revealed on associated accumulation of many elements in this mushroom. M. procera seem to possess some features of a bio-indicative species for anthropogenic Pb but also for some geogenic metals.

Effect of aquifer storage and recovery (ASR) on recovered stormwater quality variability

Aquifer Storage and Recovery (ASR) is increasingly being considered as a means of reusing urban stormwater to supplement available urban water resources. Storage of stormwater in an aquifer has been shown to affect water quality but it has also been claimed that storage will also decrease the stormwater quality variability making for improved predictability and management. This study is the first to document the changes in stormwater quality variability as a result of subsurface storage at four full scale ASR sites using advanced statistical techniques. New methods to examine water quality are required as data is often highly left censored and so traditional measures of variability such as the coefficient of variation are inappropriate. It was observed that for some water quality parameters (most notably E. coli) there was a marked improvement of water quality and a significant decrease in variability at all sites. This means that aquifer storage prior to engineered treatment systems may be advantageous in terms of system design to avoid over engineering. For other parameters such as metal(loids)s and nutrients the trend was less clear due to the numerous processes occurring during storage leading to an increase in variability, especially for geogenic metals and metalloids such as iron and arsenic. Depending upon the specific water quality parameters and end use, use of ASR may not have a dampening effect on stormwater quality variability.

Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization

The redox-induced (im)mobilization of nickel (Ni) and lead (Pb) under pre-definite redox conditions and their binding forms were studied in a periodically flooded, slightly acidic arable soil enriched with serpentine minerals at the Velika Morava River valley, Serbia. The total contents of Ni and Pb were 152 and 109 mg kg−1, respectively. Geochemical fractionation of Ni, combined with mineralogical analysis, confirmed its geogenic origin in the soil. Potentially mobile fractions were the dominating binding forms of Pb; thus, indicating anthropogenic sources as prevailing. Risk assessment indicated a low risk of Ni and Pb transfer from soil to other environmental constituents. However, the results imply that geogenic metals might pose higher environmental risk than those from anthropogenic origin, in dependence of their total concentrations and contents in the specific solid-phase fractions. Flooding of the soil was simulated in an automated biogeochemical microcosm system, which allows a control and a continuous measurements of redox potential (EH) and pH. Subsequently, the EH was increased in steps of approximately 100 mV from anoxic to oxic conditions. Concurrently, the concentrations of soluble Ni, Pb, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfates were measured. The EH was brought from low to high values (−220 to 520 mV) and correlated negative with soluble Ni, Pb, Fe, Mn and DOC. Soluble Ni ranged from 125 to 228 μg l−1 while Pb ranged from 3.0 to 21.4 μg l−1. Concentrations of both metals in solution were high at low EH and decreased with increasing EH. Nickel immobilization may be attributed to sorption to or co-precipitation with re-oxidized Fe-Mn (hydr)oxides, whereas Pb, in addition, might be immobilized via precipitation with inorganic ligands, such as carbonates and phosphates. The results imply that Ni and Pb solubility might also be related to the formation of metal-DOC complexes. The detected dynamic and mechanisms might be useful in providing critical information for assessing the potential environmental risk and creating appropriate environmental management strategies for agricultural areas enriched with Ni and Pb.

Geogenic metal mobility in a coastal inlet impacted by cannery discharge, Magdalena Bay, Baja California Sur, Mexico

Magdalena Bay is an important habitat for marine organisms, some of which have been the subject of metal bioaccumulation studies. Cannery waste is discharged into the bay providing a plausible source of contamination but this study finds that some metals occur geogenically. Bay sediments and rocks (n=59) were analyzed for total metals and clustered (HCA) into two distinct groups with PCA indicating concentrations of Cr, Cu, Mn, and Ni influenced samples near ophiolite outcrops, which reported some metal concentrations exceeding averages in the crust by an order of magnitude (up to 4450ppm Cr and 1269ppm Ni). Metals at the cannery are rarely elevated above crustal averages except Zn (max. 160ppm), however, acid-extracted Zn was below recommended sediment quality guidelines in contrast to 80% of ophiolitic samples reporting Ni extractability exceeding such guidelines. This study raises awareness of geogenic metals when considering sources of contamination in marine environments.

Analysis of heavy metals from water, sediment, and tissues of Labeo angra (Hamilton, 1822), from an Ox-box lake- an wetland site from Assam, India

ABSTRACTThe aim of this study was to assess the regional impacts of heavy metals (Mn, Fe, Mg, Ca, Cu, Zn, Cd, Cr, Pb and Ni) on water, sediment and a native, teleost fish species, Labeo angra, inhabiting a flood plain wetland of Barak River in Assam, India. Heavy metal concentrations in the water, sediments and fish were measured; bioaccumulation factor, metal pollution index as well as condition indices were calculated, to assess the pollution load and health status of the fish. Multivariate statistical analysis was used on wetland water and sediment heavy metals to ascertain the possible sources and seasonal variations of the pollutants. Results showed that most heavy metals in the wetland water and sediments exceeded the water (drinking and irrigation) and sediment quality guidelines, respectively. Seasonal variations were observed for geogenic heavy metals, Mn, Fe, Mg and Ca while no seasonal variations were observed for anthropogenic heavy metals, Cu, Cd, Cr, Pb and Ni. Multivariate statistical analysis showed that there was strong correlation between geogenic and anthropogenic heavy metals in water and sediment, both originating from the common anthropogenic sources. Accumulation of most of the metals in all the tissues was above the safe limits as recommended by the Food and Agriculture Organization. High bioaccumulation factors and metal pollution index for these metals in the different tissues revealed that metals were extensively bio-accumulated and bioconcentrated. Condition indices in fish from the wetland suggested metabolic abnormalities.

Lead (Pb) and other metals in New York City community garden soils: Factors influencing contaminant distributions

Urban gardens provide affordable fresh produce to communities with limited access to healthy food but may also increase exposure to lead (Pb) and other soil contaminants. Metals analysis of 564 soil samples from 54 New York City (NYC) community gardens found at least one sample exceeding health-based guidance values in 70% of gardens. However, most samples (78%) did not exceed guidance values, and medians were generally below those reported in NYC soil and other urban gardening studies. Barium (Ba) and Pb most frequently exceeded guidance values and along with cadmium (Cd) were strongly correlated with zinc (Zn), a commonly measured nutrient. Principal component analysis suggested that contaminants varied independently from organic matter and geogenic metals. Contaminants were associated with visible debris and a lack of raised beds; management practices (e.g., importing uncontaminated soil) have likely reduced metals concentrations. Continued exposure reduction efforts would benefit communities already burdened by environmental exposures.

Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia’s past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.

Metal Concentrations in Aggregate Interiors, Exteriors, Whole Aggregates, and Bulk of Costa Rican Soils

In many temperate soils the preferential weathering and leaching of aggregate surfaces and the nonaggregated material between aggregates depletes geogenic metals. It also shifts metals from strongly to more weakly bound metal forms. Deposited metals are sorbed preferentially on aggregate surfaces and between aggregates. We examined whether preferential desilication under tropical climate causes an enrichment in the aggregate exteriors in oxidic forms of metals. We also studied where deposited metals are bound in these soils. Aggregates (2–20 mm) were selected manually from the A horizons of eight Oxisols, six Andisols, two Mollisols, and two Inceptisols in Costa Rica. All samples were fractionated into interior and exterior portions and treated with a seven‐step sequence to extract Al, Cd, Cu, Fe, Mn, Pb, and Zn. Total concentrations of all metals except Zn were higher in the aggregate exteriors than in the interiors (average differences in % of the interior concentrations: Al, 9.0; Cd, 2.2; Cu, 8.7; Fe, 4.9; Mn, 4.2; Pb, 64.7; Zn, 0.0). The average Cd and Pb concentrations in easily extractable fractions were significantly higher in the aggregate exteriors. There were no significant differences in metal partitioning between interiors and exteriors except for Pb, which had higher proportions in extractable forms with NH2OH · HCl &gt; NH4 − acetate, pH 6.0 &gt; EDTA in the exteriors. There were few significant differences in metal concentrations and partitioning between bulk soil and whole aggregates. The results may be explained by (i) preferential desilication of the aggregate exteriors and (ii) preferential sorption of deposited heavy metals mainly in easily extractable forms.