Metals in Main Rivers of Azerbaijan: Influence of Transboundary Pollution

Silver, arsenic, cadmium, chromium, cobalt, copper, mercury, lead, and zinc were determined monthly during 2004–2008 at 11 sites in the Kura–Araks river system, Azerbaijan. Suspended fractions of the elements were studied at the five sites experiencing the highest load. Metal concentrations varied moderately at each site but differed substantially between sites. Sites near the borders with Armenia and Georgia were most polluted, both with respect to soluble concentrations and percentage transported in suspended form. Lower parts of the Kura river were shielded from metal contamination by an upstream reservoir acting as a metal trap. Corresponding removal was not evident in Araks, its main tributary, where particularly high concentrations of arsenic were observed. At the most contaminated sites, more than 60% of cadmium, cobalt, chromium, copper, manganese, nickel, lead, and zinc was transported in suspended form whereas arsenic and molybdenum occurred mainly in soluble form. Dynamics of metals in the Kura–Araks water/sediment system should be further studied to meet future problems.     

Die Wirkung der Schwermetalle Chrom,Nickel, Kupfer,Zink, Cadmium,Quecksilber und Blei auf die Aufnahme und Verlagerung von Kalium und Phosphat bei jungen Gerstenpflanzen

Effect of the heavy metals chromium, nickel, copper, zinc, cadmium, mercury and lead on uptake and translocation of K and P by young barley plants The uptake of potassium and phosphate into the roots and shoots of 7 days old barley plants from double-labelled (⁴²K, ³²P) nutrient solutions containing chromium, nickel, copper, zinc, cadmium, mercury or lead (10^?6 - 10^?4 moles/1) was measured in a constant environment after 5 hours, in order to compare early stages of toxicity. K and P uptake and translocation were inhibited by the 7 heavy metals to a different extent; K was more affected than P, and translocation of both nutrients into the shoots was more inhibited than uptake into the roots. Plants showed no visible injuries. Mercury had by far the greatest effect, zinc was almost ineffective: K uptake e.g. was reduced to 21% of the control by 10^?4 moles Hg/l, but only to 97% by the same amount of Zn, and P translocation was reduced to 8% by Hg, but was not affected by Zn. The least significant effect of Hg was detectable at a concentration of 4.10^?7 moles Hg/l ( = 0,08 ppm) in the nutrient solution, the effect of Zn only above 10^?4 moles Zn/l ( = 6,5 ppm). Arranging the tested heavy metals according to their effects leads to the sequence Hg > Pb > Cu > Cd > Cr > Ni > Zn which corresponds – apart from two deviations – to the electrochemical series of the elements.     

恩施典型富硒区土壤硒与其他元素组合特征及来源分析

硒是重要的人体和动物必需微量元素之一,在功能农业发展中起着重要的作用。为了研究高硒土壤中硒与其他元素组合特征及来源,从而支撑富硒资源的安全有效利用,本研究在恩施市沙地乡系统采集并分析了200个表层土壤样和2组土壤垂向剖面样品,运用统计学工具进行了聚类分析和因子分析。结果表明:研究区表层土壤硒含量平均值为1.88 mg/kg±2.51 mg/kg,明显高于全国表层土壤硒含量平均值。研究区土壤元素组合特征可分为三类,第一类中硒与钼、钒、铬、镉和镍等元素具有较强的伴生关系,与黑色岩系分布密切相关;第二类为三氧化二铝、铅和砷等元素/氧化物,与土壤中黏土矿物有关;第三类为钙和锶等元素,表明该同族元素的地球化学性质具有相似性。因子分析结果进一步证实了土壤硒和镉伴生主要发生在黑色岩系,不同成土母质硒等元素差异较大。     

Atmospheric Deposition of Trace Metals at Three Sites Near the Great Lakes

The concentrations of vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), cadmium (Cd), and lead (Pb) in precipitation and on airborne particles were measured at three Integrated Atmospheric Deposition Network (IADN) monitoring stations on Lakes Superior, Michigan and Erie during 1993 and 1994. These data were used to estimate annual wet and dry deposition fluxes at these sites. In most cases, both wet and dry deposition make an important contribution to the total atmospheric flux of trace metals. Total (wet + dry) annual loadings of Zn and Cr are higher at the Lake Erie site than at the Lake Michigan and Lake Superior sites. Atmospheric loadings of the other metals are similar at all three sites. Wet deposition of metals is more closely related to precipitation amount than to the concentration of metals in the precipitation. Dry deposition fluxes are controlled by the concentration of trace metals on large particles. Total particle mass concentrations are higher during the summer and fall at the Lake Erie site, however no seasonal trends in total particle mass at the other sites or trace metals at any of the sites were detected. The total atmospheric loadings calculated in this work are in agreement with other estimates of metals deposition to the Great Lakes.     

Comparison of New Ultrasonic Digestion Approaches for Plant Matrices in the Analysis of Trace Metals by Inductively Coupled Plasma–Optical Emission Spectroscopy Analysis: Contrast with USEPA Method 3050B

An ultrasonic method using two approaches, A and B, along with a reference Environmental Protection Agency (EPA) Method 3050B [i.e., a mixture of 30 mL of nitric acid–hydrochloric acid–hydrogen peroxide–water (HNO₃-HCl-H₂O₂-H₂O)] were contrasted for leaching of a plant matrix. The trace metals were arsenic, cadmium, cobalt, chromium, copper, mercury, manganese, nickel, lead, selenium, and zinc (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Se and Zn) and quantified by ICP-OES followed by an investigation into residue formation and the impact of digestion time. Approach B was the most accurate and precise with percent recoveries ranging between 99 and 120%, whereas ultrasonic approach A and the USEPA method 3050B gave similar results with poor accuracies and precisions. In the optimization of the digestion time using approach B, the total metal recovery was fairly the same over a period of 120 min except for Cr and Cu, which showed slight variations.     

Long-Term Inorganic Fertilization Effect on the Micronutrient Density in Soil and Rice Grain Cultivated in a South Korean Paddy Field

Soil fertility exerts a direct influence on the essential micronutrient contents of food crops. The focus in this study was on the role that long-term inorganic fertilization (nitrogen (N), phosphorous (P) and potassium (K)) plays in increasing the micronutrient output of the paddy cropping system. After more than 45 years of inorganic fertilizer application, the combined application of fertilizers (PK > NP > NK) substantially increased As (arsenic), B (boron), Cd (cadmium), Co (cobalt), Cr (chromium), Cu (copper), Fe (iron), Mn (manganese), Mo (molybdenum), Ni (nickel), Se (selenium), V (vanadium) and Zn (zinc) density in the soil and rice grain. Optimized and continuous application of PK fertilizers increased the overall micronutrient densities in rice milling fractions (grain and bran). Micronutrient concentrations were usually the highest in bran. Both grain and bran were rich in Fe, Mn and Zn. Correlation analysis indicated that soil pH and organic matter exert a significant and direct effect on the micronutrient concentration of rice. Although long-term fertilization enhanced the proportion of micronutrients in rice grain, the levels were still much lower than the recommended dietary intake levels for micronutrients. We therefore suggest high consumption levels of brown rice (with micronutrient-dense bran layer) because they may increase the daily intake level of micronutrients and meet the nutritional requirements that people need for sound health.     

Determination of Major and Trace Elements in Plant Samples by Inductively Coupled Plasma–Mass Spectrometry

The determination of several trace elements [arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), and lead (Pb)] in plant samples using inductively coupled plasma–mass spectrometry (ICP‐MS) was evaluated. It was established experimentally that moderate amounts (0.2–2%) of dissolved solids decreased the analyte signals significantly. Internal standardization with Rh was efficiently used to compensate for these matrix effects. The accuracy of the method was verified using reference materials digested according to two different procedures: dry ashing and microwave digestion. No significant differences were observed between measured concentrations and certified values. The investigation was next extended for the determination of major elements [aluminum (Al), boron (B), calcium (Ca), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), phosphorus (P), and zinc (Zn)] on the same reference materials. The ICP‐MS values agree well with the values supplied. However, it appeared that Sc was the most useful internal standard for major elements.     

Schwermetalle in Oberböden des Warthetals unter städtischem Einfluß

Heavy metals in surface soils of the Warta river valley in an urban area In the urban area of the city of Poznan the contamination with heavy metals was investigated. From the top soil layers of five cross-sections of the valley of the Warta river 87 samples were collected. Beside common soil characteristics the contents of arsenic, barium, cadmium, chromium, copper, iron, lead, manganese, phosphorus and zinc were analyzed. Predominantly the level of contamination with heavy metals is low in the valley soils. A higher level was found in the area of the old city centre. Especially the contents of lead, copper and zinc were raised. Downstream of the sewage plant discharge into the river Warta increased contents of lead and cadmium were found. The distribution of heavy metals in the river Warta sediments indicates that the reason of the local increase of heavy metal contents is the sewage water discharge, Correlations between the content of different heavy metals and other soil properties (pH, clay and P-content, C/N-ratio) were calculated.     

Heavy Metal Pollution by Atmospheric Transport in Natural Soils from the Northern Part of Eastern Carpathians

The present paper is a study of the heavy metal contamination ofnatural soils due to atmospheric transport in the northern partof Eastern Carpathians. The study area is located north of BaiaMare, the main Romanian centre for processing complex sulphideores. Ten undisturbed soil profiles of andosols and andic soilswere investigated. The distribution of heavy metals (Pb, Cu, Zn,Mn, Ni, Co, Cr and Cd) was studied along the soil profile and atspecific distances from the pollution sources. In addition tothe total nitric acid soluble fraction of the metals, amounts oflead, copper, zinc and manganese extractable with 0.05 Mhydrochloric acid were determined to evaluate the fraction ofeach metal potentially available to plants. Surface soils in theIgnis Mountains (10 km from Baia Mare) were more polluted withlead (200–800 ppm), with the concentration decreasing withdistance from the processing plants. Lower lead concentrationswere observed in the deeper soil horizons. The fraction of leadextractable in 0.05 M hydrochloric acid was generally higher athigh total concentrations of lead. From its geographical andsoil profile distributions it is also evident that cadmium wasalso supplied in appreciable amounts to the topsoil from thesame polution sources, whereas the trend was weaker for zincand chromium and not evident for copper, manganese, nickel, orcobalt. The fraction extractable with 0.05 M hydrochloric acidgenerally followed the order Pb > Cu > Zn > Mn.     

Vertical Distributions of Trace Metals in Natural Soil Horizons from Japan. Part 1. Effect of Soil Types

To predict the long-term behavior of trace metals in a soilprofile, we studied the vertical distributions of barium, zinc,copper, chromium, nickel, cobalt, lead, and the principalmetals, aluminum, iron and manganese, in three soils withdeveloped horizons obtained from rural areas in Japan. Totalelement analysis and selective extraction tests with variousreagents were conducted to clarify the extractability of themetals at each sampling depth.Soil-b (Dystric Cambisols) had the highest extractability ofelements although the vertical distributions of its traceelements were similar to those of soil-d (Umbric Andosols),which had to lowest metal extractability of the three soils.Soil-KUR (Orthic Acrisols or Dystric Cambisols) was the oldest of the three soils and showed downward movement of some tracemetals (chromium and nickel) and principal elements (Fe and Mn)that was probably induced by long-term weathering.The extractability of manganese, zinc and barium with water washigher than other metals examined in all three soils. Lead andcobalt in soil-b and soil-KUR also were considered to have highextractability under long-term weathering processes. Zinc andlead accumulated near soil surface showed higher extractabilitywith every reagent used than those in deep layers of the three soils.     

The effect of different production systems on the content of micronutrients and trace elements in potato tubers

The aim of this study was to determine the effect of different production systems (conventional, integrated and organic) on the content of micronutrients and trace elements in the tubers of very early, early and medium-early maturing potato cultivars. Five Polish potato cultivars were grown in three production systems under field conditions. In plant material selected microelements (chemical elements essential for living organisms) were analysed: boron (B), copper (Cu), iron (Fe), manganese (Mn) and zinc (Zn) as well as some trace elements (not regarded as essential element for living organisms): chromium (Cr), nickel, (Ni) and lead (Pb). The content of micronutrients and trace elements in potato tubers was modified by production system, genotype and weather conditions during the growing season. Organically grown potatoes had a higher content of B (8.6–8.9?mg kg^?1) and Cu (2.8–3.1?mg?kg^?1), and a lower content of Fe (47.0–47.1?mg?kg^?1), Mn (6.0–6.4?mg?kg^?1) and Zn (11.9–12.2?mg?kg^?1), than potatoes grown in conventional and integrated systems. Potatoes grown in the conventional system had the highest Pb content. Organic cultivation can assure better alimentation of potato tubers with B and Cu, which are important microelements often deficient in the soils. On the contrary, when cultivating potato in conventional system, one should supply this element with fertilisers.     

Effect of Application of Chromium Feedstock Compost on the Growth and Bioavailability of Some Trace Elements in Lettuce

A pot experiment was conducted to investigate the effect of chromium compost (0, 10, 30, and 50%) on the growth and the concentrations of some trace elements in lettuce (Lactuca sativa L.) and in the amended soils. Compost addition to the soil (up to 30%) increased dry matter yield (DMY); more than 30% decreased DMY slightly. The application of compost increased soil pH; nitric acid (HNO₃)–extractable copper (Cu), chromium (Cr), lead (Pb), and zinc (Zn); and diethylenetriaminepentaacetic acid (DTPA)–, Mehlich 3 (M3)–, and ammonium acetate (AAc)–extractable soil Cr and Zn. The addition of Cr compost to the soil increased tissue Cr and Zn but did not alter tissue cadmium (Cd), Cu, iron (Fe), manganese (Mn), nickel (Ni), and Pb. The Cr content in the lettuce tissue reached 5.6 mg kg^?1 in the 50% compost (326 mg kg^?1) treatment, which is less than the toxic level in plants. Our results imply that compost with high Cr could be used safely as a soil conditioner to agricultural crops.     

Examining the Effects of the Destroying Ammunition,Mines and Explosive Devices on the Presence of Heavy Metals in Soil of Open Detonation Pit; Part 2: Determination of Heavy Metal Fractions

As a result of the destruction of ammunition, mines, and explosive devices by the method of open detonation, the increased concentration of heavy metals is often recorded in the soil of military polygons, which is a serious ecological problem. However, in order to determine the potential risk of such locations to the environment, it is necessary to determine, in addition to the total content, the forms in which the metals are present. In this paper, a sequential extraction method was used to analyze the six fractions of five heavy metals (cadmium, lead, nickel, copper, and zinc) in the soil of the polygon for destruction of ammunition, mines, and explosive devices. Samples were collected from the place of direct detonation (so-called pits) and from the edge of the pit. The aim of this research is determination of metal speciation in order to obtain a better insight in their mobility and risk arising from this. The results showed that heavy metals are predominantly present in the residual, oxide, and organic fractions. Cd and Cu were also significantly present in the mobile fractions due to conducted activities on the polygon. To assess the potential environmental risk of soil, the risk assessment code (RAC) and individual (ICF) and global (GCF) contamination factors were used. According to the RAC, the mobility and bioavailability of the analyzed heavy metals decreases in the following order: Cd?>?Cu?>?Zn?>?Pb?>?Ni. ICF results show low to moderate risk, while GCF results show low risk in terms of heavy metal contamination in the examined area.     

石灰岩土中微量元素的含量与分布

我国南方广西、贵州和云南省境内分布着大面积的石灰岩山地丘陵,在四川、湖北、湖南、江西、广东等省也有一定面积的石灰岩山丘地区.各地的石灰岩均为泥盆纪—三迭纪的沉积灰岩.     

Assessment of Atmospheric Heavy Metals by Moss Monitoring with Isothecium Stoloniferum Brid. in the Fraser Valley, B.C., Canada

The atmospheric heavy metal pollution of the Fraser Valley, B.C., Canada was assessed in 1993 by analyzing 62 samples of the common woodland moss Isothecium stoloniferum for lead, cadmium, nickel, zinc, chromium, and manganese. The latter two metals did not show a distinct regional distribution, but lead, cadmium, nickel, and zinc showed distinct pattern along a west-east gradient. High values were found in the metropolitan Vancouver area, located in the west of the study region. Significantly lower values were recorded for mosses from the eastern more rural areas of the Fraser Valley. Metal pollutants are likely to be contained close to their emission sources by alternating south-east, north-west winds. Highest values overall were found in the North Shore Mountains, adjacent to Vancouver. This was related to higher precipitation and short range pollutant transport from the industrialized, heavily populated areas in the floodplain of the Fraser River.     

Trace element analyses of fertilizers and soil amendments by axial‐view inductively‐coupled plasma atomic emission spectrophotometry

Abstract

The application of fertilizers and other amendments, including urban and industrial wastes, to agricultural lands is of some concern due to the possibility of soil pollution by heavy metals and, ultimately, deterioration of the environment. Easy, rapid, and safe analytical procedures are therefore required to assess the potential hazard of applying these materials to soils. The objective of this study was to evaluate the potential of axial‐view inductively‐coupled plasma atomic emission (ICP‐AES) for the determination of 17 elements of environmental significance in HNO₃ and HF digests of selected fertilizers and soil amendments. Reliable results were obtained for silver (Ag), barium (Ba), beryllium (Be), cadmium (Cd), and nickel (Ni). The arsenic (As), manganese (Mn) and vanadium (V) analyses were virtually problem free in samples containing low to moderate amounts of chromium (Cr), Ni, and titanium (Ti). Bismuth (Bi), selenium (Se), and thallium (Tl) could not be determined due to spectral interferences and cobalt (Co), Cr, copper (Cu), lead (Pb), antimony (Sb), and zinc (Zn) results were of intermediate quality. Correction of spectral interferences using the multi‐component spectral fitting (MSF) technique was only partially useful for Co and Pb and not necessary or beneficial for other analytes. Axial‐view ICP‐AES is a suitable tool for the routine analyses of trace elements in fertilizers and soil amendments, and its scope could be extended to more analytes provided that more detailed interference studies are carried out. The use of the interelement correction technique (IEC), which was not tested in this study, might be helpful in correcting spectral interferences. The analyte detection limits ranged from <0.7 to 17 μg L^‐1.     

Soil Surface Geochemical Anomaly Around the Copper-Nickel Metallurgical Smelter

The soils were sampled from the center of airborne contamination caused by long time activity of a copper/nickel smelter complex in the Kola Peninsula, Russia. The soil specimens were taken from an area about 250 km², which included the town of Monchegorsk, with frequency of 1 sample (plot) per 3 km² and heavy metals nickel, copper, cobalt, chromium, lead, cadmium, strontium, iron, manganese and arsenic were measured. The soil surrounding the Smelter, including the inhabited territory of the town, was found to be contaminated by nickel and copper to levels 450- and 250 times higher in comparison to the background, respectively. These soils were found to be extremely toxic and represented a severe threat to human health. Elevated concentrations of iron and arsenic caused by smelter emissions were found too.     

Short- and long-term effects of heavy metals on urease activity in soils

Summary The inhibitory effects of cadmium, chromium, copper, lead, nickel and zinc on urease activity of five different soils during two different periods were investigated, in order to obtain information on the change in heavy metal toxicity with time. The results are presented graphically as logistic dose-response curves. When the ecological dose range was used as a measure of toxicity this value decreased significantly only for copper in the sandy soil. Considering toxicity as the ecological dose-50% (ED50) value, toxicity tended to increase over 1 1/2 years for cadmium, copper and zinc. For nickel and lead, however, the toxicity stabilized in all soils, except in sand and clay. The average ED 50 value of zinc varied between 100 and 300 mg kg^–1 and its toxicity was highest. It is emphasized that these data may help to set limits for the heavy-metal pollution of soils.     

Deposition of Heavy Metals to the Convention Waters of the Oslo and Paris Commissions

The deposition of heavy metals (arsenic, cadmium,copper, chromium, nickel, lead and zinc) on the Convention Watersof the Oslo and Paris Commissions (OSPARCOM) were calculated usingan emission based modelling approach. Emissions were taken from theUN-ECE/OSPARCOM/HELCOM Emission Inventory of Heavy Metals andPersistent Organic Pollutants. The atmospheric transport modelEUTREND was used to calculate the transport and deposition of heavymetals on the convention waters. Results were obtained for theregions Greater North Sea, Celtic Sea, Bay of Biscay and IberianCoast and for parts of the regions Arctic Waters and Wider Atlantic.The contributions of five major source categories to the depositionwere calculated. The contribution of OSPARCOM countries to thedeposition on the Convention Waters as well as the contribution ofthe non-OSPARCOM countries as a whole were calculated. Measured airconcentrations were underestimated by the calculations by a factorof 2–4 for arsenic, cadmium, copper, chromium and zinc. For lead andnickel the comparison was close to the 1:1 line. The underestimationis most likely due to an underestimation of the emissions. Acomparison between the input of heavy metals by atmosphericdeposition and riverine input around the North Sea as well as acomparison with other studies on the atmospheric input to the NorthSea estimated from measurements and modelling are presented.     

Heavy metals in tropical Lake Kariba,Zimbabwe

Metal mining is carried out in the drainage basin of Lake Kariba, Zimbabwe. In an attempt to assess the distribution of heavy metals in the lake ecosystem, the concentrations of chromium (Cr), cadmium (Cd), copper (Cu), lead (Pb), manganese (Mn), nickel (Ni), zinc (Zn), and selenium (Se) were analysed in the following ecosystem components at different locations in the lake; water, sediment, aquatic macrophytes, mussels, and carnivorous and herbivorous fish. Concentrations were generally in the same range as in other temperate and tropical aquatic ecosystems, except for Pb and Cd, which were higher in marcrophytes and fish from the lake. Apart from Cd, there were no signs of biomagnification and the highest levels of metals were found in the macrophytes and sediments. While metal contamination in fish is probably a combination of uptake from the food and an equilibrium with the surrounding water, the levels in macrophytes appear to be determined mainly by uptake from the sediment through the roots.