Inputs Of Zn Research Articles

Heavy metals assessment and identification of their sources in agricultural soils of Southern Tehran, Iran

A detailed investigation was conducted to evaluate heavy metal sources and their spatial distribution in agricultural fields in the south of Tehran using statistics, geostatistics, and a geographic information system. The content of Cd, Cu, Co, Pb, Zn, Cr, and Ni were determined in 106 samples. The results showed that the primary inputs of Cr, Co, and Ni were due to pedogenic factors, while the inputs of Zn, Pb, and Cu were due to anthropogenic sources. Cd was associated with distinct sources, such as agricultural and industrial pollution. Ordinary kriging was carried out to map the spatial patterns of heavy metals, and disjunctive kriging was used to quantify the probability of heavy metal concentrations higher than their recommended threshold values. The results show that Cd, Cu, Ni, and Zn exhibit pollution risk in the study area. The sources of the high pollution levels evaluated were related to the use of urban and industrial wastewater and agricultural practices. These results are useful for the development of proper management strategies for remediation practices in the polluted area.

Litterfall Dynamics Under Different Tropical Forest Restoration Strategies in Costa Rica

In degraded tropical pastures, active restoration strategies have the potential to facilitate forest regrowth at rates that are faster than natural recovery, enhancing litterfall, and nutrient inputs to the forest floor. We evaluated litterfall and nutrient dynamics under four treatments: plantation (entire area planted), tree islands (planting in six patches of three sizes), control (same age natural regeneration), and young secondary forest (7‐9-yr-old natural regeneration). Treatments were established in plots of 50 � 50m at six replicate sites in southern Costa Rica and the annual litterfall production was measured 5yr after treatment establishment. Planted species included two native timber-producing hardwoods (Terminalia amazonia and Vochysia guatemalensis) interplanted with two N-fixing species (Inga edulis and Erythrina poeppigiana). Litter production was highest in secondary forests (7.3Mg/ha/yr) and plantations (6.3), intermediate in islands (3.5), and lowest in controls (1.4). Secondary forests had higher input of all nutrients except N when compared with the plantation plots. Inga contributed 70 percent of leaffall in the plantations, demonstrating the influence that one species can have on litter quantity and quality. Although tree islands had lower litterfall rates, they were similar to plantations in inputs of Mg, K, P, Zn, and Mn. Tree islands increased litter production and nutrient inputs more quickly than natural regeneration. In addition to being less resource intensive than conventional plantations, this planting design promotes a more rapid increase in litter diversity and more spatial heterogeneity, which can accelerate the rate of nutrient cycling and facilitate forest recovery.

Geochemistry of marine sediments from inner Ría de Vigo (NW Spain)

Two sediment cores were recovered in San Simon Bay (NW Spain) in order to establish sediment accumulation rates by 210Pb and 137Cs dating and to reconstruct metal pollution history. Sediment composition was determined by X-ray Fluorescence. A main lithogenic origin was shown up. Grain size conditions radionuclide activities and element concentrations. Fine grained sediments concentrate pollutants and showed higher activities. Radionuclide profiles are affected by diagenetic processes and sedimentary disturbances, but a temporal framework could be obtained for the intertidal area, where the anthropogenic inputs of Cu, Pb and Zn started several decades ago.

Soil properties controlling Zn speciation and fractionation in contaminated soils

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.

Zn and S Doping in GaAs Selective Area Growth by Metal–Organic Vapor Phase Epitaxy

The surface reaction rate constant (ks) is one of the most important parameters in metal–organic vapor phase epitaxy (MOVPE), since it affects the growth rate and the composition of the epitaxial layer in selective area growth (SAG). It is possible to predict the properties of the epitaxial layer from the value of ks. The value of ks can be extracted through a two-dimensional numerical simulation of SAG, and it strongly depends on growth conditions. In this paper, zinc and sulfur doping in GaAs SAG are studied. It is shown that the ks of GaAs is independent of dopant input pressure at low Zn or S pressure. This implies that under these conditions, the growth rate will not be affected by doping. Furthermore, the database of ks values based on undoped GaAs-SAG can be used directly in doping processes. The ks value is reduced when Zn input pressure is of the same order of magnitude as Ga partial pressure. When the mask width is less than 100 µm, the masks will not influence ks. However, the ks value is reduced when 200 µm masks are used due to the excessive enhancement of trimethylgallium local pressure, which leads to a nonlinear reaction mode. The dopant concentration in SAG samples has been measured using secondary ion mass spectroscopy (SIMS). The effect of mask width on dopant incorporation can be simplified as the effect from Ga-species pressure. Zn concentration in the epitaxial layer is nearly independent of Ga partial pressure or the mask width. S concentration increases with increasing Ga partial pressure. These phenomena can be understood from their doping behavior and reactions. With increasing mask width, S incorporation in GaAs slightly increases, but is reduced when 200 µm masks are used. This reduction may be caused by the adsorption of S species on SiO2 masks.

An inventory of trace element inputs to agricultural soils in China

It is important to understand the status and extent of soil contamination with trace elements to make sustainable management strategies for agricultural soils. The inputs of trace elements to agricultural soils via atmospheric deposition, livestock manures, fertilizers and agrochemicals, sewage irrigation and sewage sludge in China were analyzed and an annual inventory of trace element inputs was developed. The results showed that atmospheric deposition was responsible for 43–85% of the total As, Cr, Hg, Ni and Pb inputs, while livestock manures accounted for approximately 55%, 69% and 51% of the total Cd, Cu and Zn inputs, respectively. Among the elements concerned, Cd was a top priority in agricultural soils in China, with an average input rate of 0.004 mg/kg/yr in the plough layer (0–20 cm). Due to the spatial and temporal heterogeneity of the sources, the inventory as well as the environmental risks of trace elements in soils varies on a regional scale. For example, sewage sludge and fertilizers (mainly organic and phosphate-based inorganic fertilizers) can also be the predominant sources of trace elements where these materials were excessively applied. This work provides baseline information to develop policies to control and reduce toxic element inputs to and accumulation in agricultural soils.

Local coordination of Zn in hydroxy-interlayered minerals and implications for Zn retention in soils

The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615–8600 mg/kg Zn) were evaluated by shell fitting. In Zn–HIS, Zn was octahedrally coordinated to oxygen at 2.06–2.08 Å and surrounded by Al atoms at 3.03–3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251–1039 mg/kg Zn) with acidic to neutral pH (pH 4.1–6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29–84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn–HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn–HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.

Zinc Fractionation in Contaminated Soils by Sequential and Single Extractions: Influence of Soil Properties and Zinc Content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.

Trace metal cycling in the Whau Estuary, Auckland, New Zealand

Environmental context. The accumulation of trace metals from urban runoff is a serious environmental concern. In the present paper we show that, in the case of the Whau Estuary, Auckland, New Zealand, there is a significant particulate Zn input, of which a significant amount of Zn is lost from the particulate phase into the dissolved phase within the water column, and via molecular diffusion across the water–sediment interface. The present study shows that changes in the chemical speciation of Zn, associated with changes in salinity, play a major role in regulating the recycling of this metal between the particulate and dissolved phases. Abstract. Dissolved Zn, Cd, Cu, Fe, and Pb concentrations were measured along a salinity gradient in the Whau Estuary, Auckland, New Zealand. We found a mid-salinity maximum in dissolved Zn and Cd concentrations, consistent with significant loss of these metals from the particulate phase into the dissolved phase. Changes in the chemical speciation of these two metals were coupled to changes in salinity and this was the major driver for Zn and Cd loss from particulate material. Contrastingly, Cu concentrations were conservative with salinity, whereas there was significant scavenging of Fe and Pb from the dissolved phase into the particulate phase. Analysis of sediment pore-water metal concentrations indicated a peak in Zn concentration within the suboxic layer. The peak occurred at a shallower depth than those for Mn and Fe. The concentration gradient across the sediment–water interface suggests that diffusional loss of Zn from the sediment pore water into the overlying water column was occurring. Conversely, the diffusion of Cu from the water column into the sediment pore water was likely to occur because pore-water Cu concentrations were lower than the overlying water column concentrations. The results from the present study show the importance of chemical speciation and the lability of metals attached to particulate material as potentially being a critical determinant on sediment metal concentrations.

Monitoring trace elements (Al, As, Cr, Cu, Fe, Mn, Ni and Zn) in deep and surface waters of the estuary of the Nerbioi-Ibaizabal River (Bay of Biscay, Basque Country)

Deep water samples (in contact with the sediment) were collected at eight different points of the estuary of the Nerbioi-Ibaizabal River (Bay of Biscay, Basque Country), both at low and high tides, during four sampling campaigns (May, September and December 2005 and March 2006). Superficial water was also sampled in March 2006. Temperature, pH, redox potential, dissolved oxygen and electrical conductivity corresponding to each sample were measured in situ at each sampling point using a multiparametric probe. The physico-chemical parameters found are typical of highly stratified estuaries, with an acceptable oxygenation level. After filtering and acidifying the samples, they were analysed by inductively coupled plasma/mass spectrometry (ICP/MS) to simultaneously determine the total concentration of Al, As, Cr, Cu, Fe, Mn, Ni and Zn. Concentrations in the μg kg − 1 level were found in all cases ( c Cr and c Ni, 1–10; c Al, c As and c Zn, 10–50; c Cu and c Mn, 10–100 and c Fe, 100–400 μg kg − 1 ). A probable net input of Al, Cr, Mn and Zn via the main (Nerbioi-Ibaizabal) and some of the tributary rivers (Galindo, Asua and Gobela) was identified. Evidence of a common source of Al and Zn to the estuary was found. Correlation analysis of data revealed connections between variables (concentration of Cu, Fe and As with salinity, as well as c Al with c Zn, c Cu with c Fe, c As with c Fe, and c As with c Cu). Principal Component Analysis (PCA) of data allowed the samples to be grouped according to sampling campaign, with two principal components accounting for 62% of the total variance. In addition, plots of element concentration against salinity suggested a conservative behaviour for As, Cu and Fe and a non-conservative one for Cr. Not clear mixing behaviour was observed for the rest of elements.

Highly Organic Soils as “Witnesses” of Anthropogenic Pb, Cu, Zn, and 137Cs Inputs During Centuries

Highly organic soils, and in particular ombrotrophic bogs, have been often used to reconstruct climate changes and heavy metal contaminations. Ombrotrophic peat bogs, in fact, are domed peatlands in which the surface layers are hydrologically isolated from the influence of local groundwaters and surface waters, and are supplied only by atmospheric depositions. In the present work, the attention of Authors has been focused on Pb, Cu, and Zn, coming mainly from anthropogenic activities, and 137Cs, released mostly during the Chernobyl disaster. Practically, an undisturbed peat profile was cored in 2005 from a Swiss ombrotrophic bog and analysed using energy-dispersive miniprobe multielement analyzer X-ray fluorescence and Low Background γ-ray spectrometry in order to investigate and quantify the impact of human activities (e.g., industry, traffic, combustion of fossil fuels, “environmental disasters”) in causing Pb, Cu, Zn, and 137Cs contaminations during the centuries. Obtained data show that highly organic soils in general, and ombrotrophic bogs in particular, reflect the anthropogenic inputs in heavy metal and radionuclide contaminations. In fact, these environments allowed to follow the depositional history of Pb, Cu, and Zn, both underlining a general increasing of their production since the Industrial Revolution, and remarking past single impacting events such as the introduction of leaded gasoline and of particular agricultural practices. Further, although 137Cs showed a main peak corresponding to the Chernobyl disaster, confirming the role of bogs as archive of human activity, data revealed a certain mobility of this radionuclide along the profile. Thus, highly organic soils can be considered as both “witness” of the impact of human activity during centuries and indicator of the health of our planet.

Groundwater contributions to metal transport in a small river affected by mining and smelting waste

The Riou Mort watershed, strongly affected by former coal mining and Zn ore treatment, has been the major source of the historical polymetallic pollution of the Lot–Garonne–Gironde fluvial–estuarine system. Two decades after the end of ore treatment, the former industrial area still contributes important amounts of metals/metalloids from various, partly unidentified, sources to the downstream river system. This study presents the high spatial variability of metal/metalloid (Cd, Zn, As, Sb, U, V) concentrations in water and suspended particulate matter (SPM) from eight observation sites during a short, intense flood event. Despite important dilution effects, the observed concentration levels at the different sites suggested additional Cd and Zn inputs, probably from polluted groundwater. This formerly unknown metal source was then localized and characterized by sampling water and SPM along two longitudinal profiles during different hydrological situations. Groundwater inputs of “truly dissolved” (<0.02 μm) Cd and Zn occurred along ∼200 m, contributing 43% and 28% to the total annual (2004) Cd and Zn fluxes in the Riou Mort River. The estimated groundwater concentrations of Cd and Zn (2500–6700 and 83,000–170,000 μg l −1, respectively) in the source zone were consistent with values measured in samples from the near aquifer (5400–13,000 and 200,000–400,000 μg l −1). The present work induced concrete remediation actions (pumping and treatment of the polluted groundwater), that are expected to strongly reduce dissolved Cd and Zn emissions into the Riou Mort River.

Cadmium and zinc in soil solution extracts following the application of phosphate fertilizers

This study investigated the solubility of cadmium and zinc in soils after the application of phosphate fertilizers containing those two metals. The solubility of cadmium and zinc was assessed by measuring their concentration in soil water extracts. Three monoammonium phosphate fertilizers containing various amounts of metals were applied on cultivated fields for 3 years at three different rates. In order to investigate the effects of long-term applications of fertilizers on the solubility of Cd and Zn, a similar design was used to apply contaminated fertilizers to soils in a laboratory experiment using a single fertilizer addition equivalent to 15 years of application. Phosphate fertilizers increased the concentration of Cd in soil extracts compared to control in 87% and 80% of the treatments in field and laboratory experiments respectively. Both increasing the rate of application and using fertilizer containing more Cd lead to higher Cd concentrations in extracts for the field and the laboratory experiments. The addition of the equivalent of 15 years of fertilizer application in the laboratory results in higher Cd concentration in extracts compared to the field experiment. For Zn, the fertilizer treatments enhanced the metal solution concentration in 83% of field treatments, but no significant correlations could be found between Zn inputs and its concentration in solution. In the laboratory, fertilizer additions increase the Zn concentrations in 53% of the treatments and decrease it in most of the other treatments. The decrease in Zn concentrations in the laboratory trial is attributed to the higher phosphate concentrations in the soil solution; which is presumed to have contributed to the precipitation of Zn-phosphates. For both trials, the metal concentrations in soil extracts cannot be related to the Zn concentration in the fertilizer or the rate of application. The high Zn to Cd ratio is presumably responsible for the Cd increase in the soil extracts due to competitive displacement by Zn. Finally, the observed acidification of soils with fertilizer application will also contribute to metal solubilisation.

Amendments and plant cover influence on trace element pools in a contaminated soil

A 30-month experiment was carried out in field containers to evaluate the potential of various amendments and/or a plant cover (Agrostis stolonifera L.) for reclamation of a soil contaminated with As, Cd, Cu, Pb and Zn. Five amended treatments with plant were established: leonardite (LEO), litter (LIT), municipal waste compost (MWC), biosolid compost (BC) and sugar beet lime (SL). Two controls were also set up: control without amendment but with plant (CTRP) and control without amendment and without plant (CTR). A widely accepted sequential extraction procedure was used to assess changes in trace element pools in soil following remediation. Results showed that trace element distribution in soil was highly influenced by the origin of the contamination (mine sulphides): trace elements were mainly associated with the residual fraction (in form of sulphides) and to a lesser extent with the reducible fraction, where Fe oxides and oxyhydroxides are expected, as a consequence of sulphide oxidation. The addition of amendments and/or establishment of a plant cover showed no clear effect on Cd and Pb distribution. The influence on As fractionation was also small and restricted to the most labile fraction, where higher concentrations of As were found in SL, MWC and BC. In contrast, Cu concentrations in the most labile fraction decreased in MWC, BC, LEO and LIT, while Cu recovery within the organic matter-associated fraction increased in these treatments. Zinc concentration in the most labile fraction was significantly lower in CTRP than in CTR, whereas Zn recovery in this fraction increased in MWC due to Zn input. In some cases redistribution of amendment-derived trace elements from slow-releasing fractions to the residual pool seemed to occur. Since the increase in As and Zn only accounted for a small proportion of the total pool and soil quality improved in treated soils, the use of soil amendments and/or revegetation might be a reliable option for long-term reclamation of soils moderately contaminated with trace elements. Nonetheless, high quality by-products should be employed to minimize trace element input to soil.

Zinc in plants

Zinc (Zn) is an essential component of thousands of proteins in plants, although it is toxic in excess. In this review, the dominant fluxes of Zn in the soil-root-shoot continuum are described, including Zn inputs to soils, the plant availability of soluble Zn(2+) at the root surface, and plant uptake and accumulation of Zn. Knowledge of these fluxes can inform agronomic and genetic strategies to address the widespread problem of Zn-limited crop growth. Substantial within-species genetic variation in Zn composition is being used to alleviate human dietary Zn deficiencies through biofortification. Intriguingly, a meta-analysis of data from an extensive literature survey indicates that a small proportion of the genetic variation in shoot Zn concentration can be attributed to evolutionary processes whose effects manifest above the family level. Remarkable insights into the evolutionary potential of plants to respond to elevated soil Zn have recently been made through detailed anatomical, physiological, chemical, genetic and molecular characterizations of the brassicaceous Zn hyperaccumulators Thlaspi caerulescens and Arabidopsis halleri.

Effect of Agricultural Practices on Trace‐Element Distribution in Soil

The impact of agricultural practices on the spatial distribution of trace elements (TEs) in the surface horizon of Albeluvisols was studied by comparing three types of situation with an increasing anthropogenic gradient: a forest soil, considered as a reference, and cultivated soils with and without spreading of sewage sludge. Total cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) were determined in soil surface horizons. The quantity of particles finer than 2 µm, organic carbon (OC), iron (Fe), manganese (Mn), and calcium (Ca) contents were also measured and used as tracers of soil components that may have contained TEs. Governing factors of the spatial variability of TEs were searched for through comparison of the descriptive statistics (mean and coefficient of variation) and the determination of the best multivariate model predicting TE contents. Nickel and Cr distributions seem to be mainly linked to variability of the parent material composition, whereas that of Co is related to redox pedological processes. In addition, agricultural practices play a role in TE distribution, through the input of TEs, mostly Cd, Cu, and Zn, via sewage sludge spreading and liming amendments, and lateral (homogenization) and vertical (mixing of horizons) redistribution through tilling the soil.

Organotin Compounds and Selected Metals in the Marine Environment of Northern Adriatic Sea

The extent of pollution with organotin compounds and Cd, Pb, Ni, Cu, Zn, Cr, Mn, V, Co and Al was investigated in sediments and mussels (Mytilus galloprovincialis) from the Slovenian costal area of the Northern Adriatic Sea. Sampling was performed in Marina Portoroz, Dockyard Izola, non exposed area of the Bay of Mesecev zaliv and in Mariculture Secovlje. Mussels were taken in the summer and winter time, while sediments were collected during the winter sampling. Organotin compounds were determined by gas chromatography-mass spectrometry and metals by flame or electrothermal atomic absorption spectrometry. The accuracies of the analytical procedures were checked by the analysis of standard reference materials CRM 477 mussel tissue and PACS 2 marine sediment (organotin compounds) and SRM 2976 mussel tissue and CRM 320 river sediment (metals). Good agreements between certified and determined values were obtained. Normalization procedure to Al was applied to estimate the anthropogenic inputs of metals in sediments. The analyses of sediments demonstrated moderate pollution with organotin compounds in Marina Portoroz and in Dockyard Izola. Concentrations of tributyltin species were higher than those of dibutyltin and monobutyltin. In mussels substantial contamination with tributyltin was observed in Marina Porotroz and Dockyard Izola. The extent of pollution was higher in the winter time. The analysis of metals in sediments exhibited elevated concentrations in Marina Portoroz and Dockyard Izola. Data from the normalization procedure indicated the anthropogenic inputs of Cu, Zn and Cr in Marina Portoroz and Mn in Bay of Mesecev zaliv and Dockyard Izola. Mussels, as accumulators of pollutants, in general contained higher metal concentrations during winter time in Dockyard Izola.

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn2+ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn2+ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn2+, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.

Fe, Cu, Mn, And Zn Input and Availability in Calcareous Soils Amended with the Solid Phase of Pig Slurry

A number of feed additives, such as As, Co, Cu, Fe, Mn, Zn, and Se are added to enhance pig growth and performance, but most of these micronutrients pass directly through the animal, which leads to elevated levels in the manure. An accumulation of P and trace elements, especially Zn and Cu, typically occurs with repeated swine manure application on soil. The potential environmental hazard associated with the loading of these elements in amended soils could actually be a positive fact in calcareous soils that usually show a high deficiency in available micronutrients. In this experiment, we analyzed the effect of the application of the solid phase of pig slurry to agricultural calcareous soils on the input and availability of Fe, Mn, Cu, and Zn. The experimental design was based on a field experiment using, as fertilizers two manures derived from the solid phase of pig slurry (composted, [C] and noncomposted [NC]). Two application rates were established to supply to the soils 300 and 450 kg N ha−1, respectively, using a nonamended soil as a control. Soil samples were taken at 0, 14, 33, 53, 73, and 103 days. Available Fe, Cu, Mn, and Zn were extracted with DTPA (0.005 M DTPA, 0.01 N CaCl2, and 0.1 N TEA at pH 7) and determined by using atomic absorption spectrophotometry. A significant effect of manure application on available Fe, Cu, Mn, and Zn was observed. Zn and, to a lesser degree, Fe DTPA contents in amended soils were increased by composted and noncomposted pig manure, and Mn was increased by the noncomposted material. Extractable Cu was lower in amended soils, than in the controls. In general, the composted pig manure induced less variation of the studied micronutrient contents in amended soils than the noncomposted manure.