Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage.     

Seasonal variation of heavy metals in ambient air and precipitation at a single site in Washington, DC

Atmospheric samples of precipitation and ambient air were collected at a single site in Washington, DC, for 7 months (for ambient air samples) and 1 year (for wet deposition samples) and analyzed for arsenic, cadmium, chromium and lead. The ranges of heavy metal concentrations for 6-day wet deposition samples collected over the 1-year period were 0.20-1.3 microg/l, 0.060-5.1 microg/l, 0.062-4.6 microg/l and 0.11-3.2 microg/l for arsenic, cadmium, chromium and lead, respectively, with a precision better than 5% for more than 95% of the measurements. The ranges of heavy metal concentrations for the 6-day ambient air samples were 0.800-15.7 ng/m(3), 1.50-30.0 ng/m(3), 16.8-112 ng/m(3), and 2.90-137 ng/m(3) for arsenic, cadmium, chromium and lead, respectively, with a precision better than 10%. The spread in the heavy metal concentration over the observation period suggests a high seasonal variability for heavy metal content in both ambient air and wet deposition samples.     

Seasonal and spatial distribution of metals in surface sediment of an urban estuary

Aquatic pollution by metals is of concern because of various toxic effects to marine life. The Tolka Estuary, Co. Dublin, Ireland, is a typical Irish urban estuary. It has a significant metal loading originating from the urban environment. Results of a 25month analysis of cadmium, copper, lead and zinc spatial and temporal distribution over 10 sample locations in this estuary are presented in this paper. Metal concentrations were analysed using differential pulse polarography. Significant seasonal and spatial trends in metal distribution were observed over the 25months. Sediment metal concentrations gradually increased (30-120%) in spring to a maximum at the end of summer which was followed by a decrease in winter months (30-60%). Sediment organic matter (OM) concentrations exhibited similar seasonal trends and a positive correlation between OM and metal distributions was observed, implying OM had an influence on metal distributions over time.     

Simultaneous immobilization of metals and arsenic in acidic polluted soils near a copper smelter in central Chile

Introduction  

Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined.     

Ion activity and distribution of heavy metals in acid mine drainage polluted subtropical soils

The oxidative dissolution of mine wastes gives rise to acidic, metal-enriched mine drainage (AMD) and has typically posed an additional risk to the environment. The poly-metallic mine Dabaoshan in South China is an excellent test site to understand the processes affecting the surrounding polluted agricultural fields. Our objectives were firstly to investigate metal ion activity in soil solution, distribution in solid constituents, and spatial distribution in samples, secondly to determine dominant environment factors controlling metal activity in the long-term AMD-polluted subtropical soils. Soil Column Donnan Membrane Technology (SC-DMT) combined with sequential extraction shows that unusually large proportion of the metal ions are present as free ion in the soil solutions. The narrow range of low pH values prevents any pH effects during the binding onto oxides or organic matter. The differences in speciation of the soil solutions may explain the different soil degradation observed between paddy and non-paddy soils.     

Seasonal patterns of the bacterioplankton community composition in a lake threatened by a pesticide disposal site

Background aim and scope  

The objective of the study was to determine the effects of ca. 35 years of pesticide contamination (pesticide dump—PD) of Lake Szeląg Wielki (located in the north-eastern Poland) on changes in the microbial communities of aquatic ecosystems. In the years 2008–2009, analyses were carried out for seasonal changes in the quantity and composition of bacterioplankton in the lake examined, which is of high significance to the tourism and fishing industries and is located in the vicinity of an area subjected to reclamation after a pesticide dump.     

Progression of natural attenuation processes at a crude oil spill site: II. Controls on spatial distribution of microbial populations

A multidisciplinary study of a crude-oil contaminated aquifer shows that the distribution of microbial physiologic types is strongly controlled by the aquifer properties and crude oil location. The microbial populations of four physiologic types were analyzed together with permeability, pore-water chemistry, nonaqueous oil content, and extractable sediment iron. Microbial data from three vertical profiles through the anaerobic portion of the contaminated aquifer clearly show areas that have progressed from iron-reduction to methanogenesis. These locations contain lower numbers of iron reducers, and increased numbers of fermenters with detectable methanogens. Methanogenic conditions exist both in the area contaminated by nonaqueous oil and also below the oil where high hydrocarbon concentrations correspond to local increases in aquifer permeability. The results indicate that high contaminant flux either from local dissolution or by advective transport plays a key role in determining which areas first become methanogenic. Other factors besides flux that are important include the sediment Fe(II) content and proximity to the water table. In locations near a seasonally oscillating water table, methanogenic conditions exist only below the lowest typical water table elevation. During 20 years since the oil spill occurred, a laterally continuous methanogenic zone has developed along a narrow horizon extending from the source area to 50-60 m downgradient. A companion paper [J. Contam. Hydrol. 53, 369-386] documents how the growth of the methanogenic zone results in expansion of the aquifer volume contaminated with the highest concentrations of benzene, toluene, ethylbenzene, and xylenes.     

Sources and pathways of artificial radionuclides to soils at a High Arctic site

Activity concentrations, inventories and activity ratios of ¹³⁷Cs, ²³⁸Pu, ^239?+?240Pu and ²⁴¹Am in soil profiles were surveyed in the dry tundra and the adjoining proglacial zones of glaciers at a High Arctic site on Svalbard. Vertical profiles of radionuclide activities were determined in up to 14-cm-thick soil sequences. Additionally, soil properties (pH, organic matter, texture, mineral composition and sorption capacity) were analyzed. Results obtained in this study revealed a large range of activity concentrations and inventories of the fallout radionuclides from the undetectable to the uncommonly high levels (inventories of 30,900?±?940, 47?±?6, 886?±?80 and 296?±?19 Bq/m² for ¹³⁷Cs, ²³⁸Pu, ^239?+?240Pu and ²⁴¹Am, respectively) found in two profiles from the proglacial zone. Concentration of these initially airborne radionuclides in the proglacial zone soils is related to their accumulation in cryoconites that have a large ability to concentrate trace metals. The cryoconites develop on the surface of glaciers, and the material they accumulate is deposited on land surface after the glaciers retreat. The radionuclide inventories in the tundra soils, which effectively retain radionuclides due to high organic matter contents, were comparable to the global fallout deposition for this region of the world. The ²³⁸Pu/^239?+?240Pu activity ratios for tundra soils suggested global fallout as the dominant source of Pu. The ²³⁸Pu/^239?+?240Pu and ^239?+?240Pu/¹³⁷Cs activity ratios in the proglacial soils pointed to possible contributions of these radionuclides from other, unidentified sources.     

Copper uptake by Elsholtzia splendens and Silene vulgaris and assessment of copper phytoavailability in contaminated soils

Tolerance and metal uptake are two essential characteristics required for phytoextraction of metals from contaminated soils. We compared tolerance and Cu uptake of Elsholtzia splendens (reported previously to be a Cu hyperaccumulator) with Silene vulgaris (the Imsbach population, a well-known Cu-tolerant excluder species), using 30 soils varying widely in total Cu concentration (19-8645 mg kg(-1)). We further investigated the effectiveness of different soil testing methods for predicting plant metal uptake. The results showed that both Elsholtzia splendens and Silene vulgaris were tolerant to Cu, especially Silene vulgaris. However, Elsholtzia splendens did not hyperaccumulate Cu, but behaved as a typical Cu excluder like Silene vulgaris. The concentrations of Cu in both plants correlated more closely with 1 M NH4NO3 extractable Cu, soil solution Cu, or effective Cu concentration determined using DGT, than with soil total Cu, EDTA extractable Cu or free Cu2+ activity. The relationships between soil solution properties and root Cu concentrations were further investigated using multiple regression. The results showed that increasing soil solution pH increased root Cu concentration when free Cu2+ activity was held constant, suggesting a higher phytoavailability of free Cu2+ at a higher pH. Soil solution DOC appeared to play two contrasting roles on the phytoavailability of Cu: (1) reducing Cu availability by complexing Cu; and (2) increasing Cu availability at the same level of free Cu2+ activity by providing a strong buffer for free Cu2+. The results are consistent with the intensity/capacity concept for phytoavailability of metals in soils.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Growth response and phytoextraction of copper at different levels in soils by Elsholtzia splendens

Phytoremediation is a promising approach for cleaning up soils contaminated with heavy metals. Information is needed to understand growth response and uptake mechanisms of heavy metals by some plant species with exceptional capability in absorbing and superaccumulating metals from soils. Greenhouse study, field trial, and old mined area survey were conducted to evaluate growth response and Cu phytoextraction of Elsholtzia splendens in contaminated soils, which has been recently identified to be tolerant to high Cu concentration and have great potential in remediating contaminated soils. The results from this study indicate that the plant exhibited high tolerance to Cu toxicity in the soils, and normal growth was attained up to 80 mg kg(-1) available soil Cu (the NH4OAc extractable Cu) or 1000 mg kg(-1) total Cu. Under the field conditions, a biomass yield of 9 ton ha(-1) was recorded at the soil available Cu level of 77 mg kg(-1), as estimated by the NH4OAc extraction method. Concentration-dependent uptake of Cu by the plant occurred mainly at the early growth stage, and at the late stage, there is no difference in shoot Cu concentrations grown at different extractable soil Cu levels. The extractability of Cu from the highly polluted soil is much greater by the roots than that by the shoots. The NH4OAc extractable Cu level in the polluted soil was reduced from 78 to 55 mg kg(-1) in the soil after phytoextraction and removal of Cu by the plant species for one growth season. The depletion of extractable Cu level in the rhizosphere was noted grown in the mined area, even at high Cu levels, the NH4OAc extractable Cu in the rhizosphere was 30% lower than that in the bulk soil. These results indicate that phytoextraction of E. splendens can effectively reduce the plant-available Cu level in the polluted soils.     

Elevational patterns of sulfur deposition at a site in the Catskill Mountains,New York

In this paper we report measurements of SO^2-₄ fluxes in throughfall and bulk deposition across an elevational transect from 800 to 1275 m on Slide Mountain in the Catskill Mountains of southeastern New York State. The net throughfall flux of SO^2-₄ (throughfall-bulk deposition), which we attribute to cloud and dry deposition, increased by roughly a factor of 13 across this elevational range. Part of the observed increase results from the year-round exposure of evergreen foliage at the high-elevation sites, compared to the lack of foliage in the dormant season in the deciduous canopies at low elevations. Comparison of the net throughfall flux with estimates of cloud deposition suggests that both cloud deposition and dry deposition increased with elevation. Dry deposition estimates from a nearby monitoring site fall within the measured range of net throughfall flux for SO^2-₄. The between-site variation in net throughfall flux was very high at the high-elevation sites, and less so at the lower sites, suggesting that studies of atmospheric deposition at high-elevations will be complicated by extreme spatial variability in deposition rates. Studies of atmospheric deposition in mountainous areas of the eastern U.S. have often emphasized cloud water deposition, but these results suggest that elevational increases in dry deposition may also be important.     

Effect of soil pH on availability to crops of metals in sewage sludge-treated soils. I. Nickel, copper and zinc uptake and toxicity to ryegrass

The effect of soil pH value on concentrations of Ni, Cu and Zn in ryegrass grown on two sludge-treated soils was examined under field conditions and the maximum permissible soil limit values for these elements were determined which prevent phytotoxicity in crops where sewage sludge is applied to agricultural soils with pH <6.0. Concentrations of all the elements in ryegrass decreased as simple linear functions of increasing soil pH and this response was consistent across the range of pH values measured (pH 4.2-7.0). The response of individual elements tended to differ though, with Cu being less sensitive to changing pH conditions compared with Zn and Ni which responded in a similar manner. The yield of ryegrass also increased with increasing soil pH value probably due to the effects on Zn uptake as the crop content of Zn exceeded known upper critical tissue concentrations for this element at both sites. The proportional change in metal content of ryegrass at pH 5.0, 5.5 and 7.0 from tissue concentrations at pH 6.0 was calculated to determine the permissible soil concentration values on the basis of current maximum limits set by the Sludge Regulations in the UK for sludge-treated agricultural land at pH 6.0-7.0. The estimated permissible concentrations of Ni and Zn in soil corresponded with the regulatory values at the low pH ranges, but were substantially above the current soil limits at pH 7.0 indicating larger quantities of these elements could be safely applied under alkaline soil conditions. The estimated soil limits for Cu implied that the current Regulations were highly precautionary for this element.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.     

Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation

Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures.     

Seasonal concentrations and partitioning of PAHs in a suburban site of Bursa, Turkey

Effects of space heating on atmospheric concentrations and gas-particle partitioning of PAHs were investigated in a suburban site of Bursa, Turkey. The average concentrations of ∑₁₅-PAHs in heating season samples were approximately 10 times higher than those of non-heating season samples. The plot of log K_p versus log P_L⁰ for all the data set gave significantly different slopes. The slope for the heating season (−0.75) samples was steeper than the one for the non-heating season (−0.64) samples. It was also observed that partitioning of PAHs for the non-heating season samples showed different characteristics depending on air parcel trajectories. Generally steeper slopes were obtained for the air parcels traveled across the Black sea and arrived to the sampling site from northern sector. On the other hand, the variations in slopes according to air mass origin were insignificant for the heating season samples. Local contributions from space heating are the reason for this observation.     

某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况,对该矿区东河流域附近重金属污染源进行了调查,同时,对地下水和土壤样品进行了采样分析,结果表明：（1）该矿区东河流域附近的主要污染源有18个,其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源;（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995）,综合污染指数P综〉1,该矿区主要的重金属污染元素为Cd、As和Hg,且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系;（3）重金属元素在土壤中的纵向迁移不明显,该矿区附近20个采样点的地下水并未受到污染,综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Compartmentation of metals in foliage of Populus tremula grown on soils with mixed contamination. II. Zinc binding inside leaf cell organelles

The phytoextraction potential of plants for removing heavy metals from polluted soils is determined by their capacity to store contaminants in aboveground organs and complex them safely. In this study, the metal compartmentation, elemental composition of zinc deposits and zinc complexation within leaves from poplars grown on soil with mixed metal contamination was analysed combining several histochemical and microanalytical approaches. Zinc was the only heavy metal detected and was stored in several organelles in the form of globoid deposits showing β-metachromasy. It was associated to oxygen anions and different cations, noteworthy phosphorous. The deposit structure, elemental composition and element ratios indicated that zinc was chelated by phytic acid ligands. Maturation processes in vacuolar vs. cytoplasmic deposits were suggested by differences in size and amounts of complexed zinc. Hence, zinc complexation by phytate contributed to metal detoxification and accumulation in foliage but could not prevent toxicity reactions therein.     

Effect of soil pH on availability to crops of metals in sewage sludge-treated soils. II. Cadmium uptake by crops and implications for human dietary intake

Appropriate pH-related permissible soil-limit concentrations for cadmium in sewage sludge-treated agricultural soils were estimated from the proportional changes in concentrations of cadmium in potatoes, oats and ryegrass grown on two sludge-amended soils and at different pH values. Implications for potential human dietary intake of cadmium were also assessed. Yields of crops increased with increasing soil pH, probably in response to decreasing uptake of zinc as soil pH value was raised. In general, cadmium concentrations in peeled potato tubers, potato peelings, oat straw and ryegrass decreased as simple linear functions of increasing soil pH over the range of pH values measured (pH 3.9-7.6). Cadmium concentrations in potato peel were particularly sensitive to changing pH conditions, whereas cadmium levels in oat grain were independent of soil pH. On the basis that a highly precautionary approach is adopted in setting soil standards for heavy metals, appropriate permissible concentrations of cadmium in sludge-treated agricultural soil which protect the human food chain were determined as 2.0 and 2.5 mg Cd Kg(-1) for banded pH ranges of 5.0-5.5 and 5.5-6.0, respectively.