Accumulation and metal fluxes in the central Venice Lagoon during the last century

Samples from 18 short sediment cores were analyzed for major and trace metals (Al, Fe, Ca, K, Mg, Mn, Si, Ti, Pb, Zn, Cu, Ni, and Cr), ²¹⁰Pb, ¹³⁷Cs, total organic carbon, grain size, and mineralogical composition to find the record of major environmental changes, either natural or anthropogenic, and to establish their chronologies. Some sediments are characterized by nearly constant composition over time, but others clearly show signs of an increasing marine influence, as an increase of the carbonate contents, after the opening of the Malamocco-Marghera Canal in 1969. These changes sometimes obscure the real pattern of pollutants and tracers, which is revealed by normalization against Al. Zn is the most important contaminant, with concentration factors up to 9.3 times the background level, and the most contaminated sediments are those within a few kilometers from the industrial district of Porto Marghera. ²¹⁰Pb activity-depth profiles were used to calculate apparent accumulation rates that provide a basis for the assessment of metal fluxes. The sediments of several sites show a significant increase in anthropogenic metal contamination starting from the second decade of last century, with maximum inputs from 1930 to 1970. The decrease of heavy metal concentrations observed in surficial sediments of some sampling sites could be related to a recent reduction of pollutant inputs.     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^-1) on ¹³⁷Cs adsorption-desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26-99.97%) of added ¹³⁷Cs (3.7 × 10³-7.03 × 10⁵ Bq l^-1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K_ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K_ads and soil pH was observed. The ¹³⁷Cs adsorption-desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09-0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Elemental composition of Sal forest soils around Chhotanagpur Plateau,India

In recent decades, the Sal-dominated tropical deciduous forests (TDFs) were experiencing loss of regeneration due to lack of seed germination of native species. To understand this ecological problem, the present study dealt with the spatial and temporal variations in biogeochemical parameters of Sal forest soils. Twenty soil samples were collected from four TDF sites in the Chota Nagpur Plateau, India. The inventories of tree species in three life-cycle stages (seedling, sapling and adult) were carried out in four sites. Site-I (290?stems?ha^?1) showed occurrence of only one species (Shorea robusta) without seedling and sapling. The pH of forest soils was acidic to slightly acidic in nature. Seasonal variations in C/N ratio showed rapid mineralization of organic matter in the rainy season. ANOVA revealed that the degree of seasonal variation caused significant difference in pH, soil organic carbon, soil organic matter, total carbon, Al, Fe, Ca, Mg, Mn and P across four sites. The strong correlation of P with pH, Al, Fe, Mg and Mn indicated highly oxidised and exchangeable nature of dry forest soils. Factor analysis of soil parameters revealed that the different combinations of edaphic conditions in different seasons were important in the distribution of the dry tropical forests communities in Chota Nagpur Plateau.     

南京城市土壤中重金属的化学形态分布

采取Tessier连续提取法，研究了南京市不同城区表层土壤中Fe,Mn,Cr,Ni,Co,V,Cu,Zn,Pb的化学形态分布。结果表明，南京城市土壤中Fe,Mn,Cr,Ni,Co,V,Zn,Pb以残渣晶格态为主，可交换态比例极低；Cu在城市道路旁的土壤中有机物结合态所占的比例最高，其他区域残渣晶格态所占的比例最高，与非城区自然土壤相比，主要来源于人为输入的Mn,Cu,Zn,Pb残渣晶格态所占的比例低，活性态比例大；Cr和主要来源于原土壤物质的Fe,Ni,Co,V在城市土壤与非城区自然土壤中各形态所占的比例相似，残渣晶格态比例大，活性态比例极低。     

Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

不同母质发育的水稻土中铁、锰对甲烷排放的影响

盆栽结果表明,不同土壤类型铁、锰含量的差异是造成不同土壤类型间甲烷排放量差异甚大的重要因素之一。土壤中铁、锰通过对土壤氧化还原电位及根膜形成的影响而影响甲烷的排放。     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

砂页岩赤红壤磷肥活化效果及其机理研究

应用不同活化剂处理不同性质的磷肥，并对其在砂页岩赤红壤中的生物效应及作用机理进行了研究。结果表明，在砂页岩赤红壤上，施用供试的儿种经活化剂处理的磷肥均能显著提高蔬菜生物量。砂页岩赤红壤中的铁、锰质量分数与磷素的有效性有密切的关系，且在还原条件下，土壤铁、锰对磷的固定作用更大；硅、钙可促进土壤中磷的释放。供试活化剂不仅可促进难溶磷的释放，还可控制水溶性磷的释放，使土壤供磷性能平稳；有机活化剂的用量，用于难溶性磷促释时其质量分数为3％，用于水溶性磷控释时其质量分数约为14％。在土壤-植物体系中，活化剂对磷的促释和控释机理是它通过对土壤铁、锰、铝质量分数的调节而实现对磷的活化。     

Ökotoxikologische Untersuchung von Sedimenten und Schwebstoffen

The potential risk of ground-water contamination through the infiltration of contaminants originating from suspended matter and sediments deposited within flood retention areas in the Upper Rhine valley, as well as subsequent problems for drinking water production, were analyzed by means of the bacterial dehydrogenase activity (DHA; sediment contact test) assay with Arthrobacter globiformis and in a prolonged embryo toxicity assay using zebrafish (Danio rerio). Since the direct uptake of contaminants from particle-bound sources has usually been assumed to play only a minor role in bioaccumulation, the availability of organic extracts to biota has generally been regarded as being overestimated. In order to confirm or discard this hypothesis, organic (acetone) extracts of recently suspended, freeze-dried matter, as well as freeze-dried sediments collected from Rhine flood plains (i.e. soil samples) were compared to corresponding native samples in order to screen for the relative availability of particle-bound contaminants. Whereas a significantly higher ecotoxicological burden was observed for some native soil samples, organic extracts of suspended matter proved to be more toxic than corresponding native samples when compared to organic extracts using each test system. With respect to organic extracts, the suspended matter samples were more toxic than soil samples taken from a rarely flooded site. In contrast to the native samples, the rarely flooded soils revealed a higher toxicity than suspended matter. Therefore, organic extracts did not necessarily overestimate the toxicity of soil and suspended matter samples. Moreover, considerable toxicity of particle-bound contaminants to both bacteria and fish embryos, even in native samples, corroborate the hypothesis that particle-bound contaminants may be more readily available than is generally assumed.     

土壤酸化与油菜锰毒关系研究

对湖北省的主要旱地土壤种植多茬作物后油菜生产锰毒的原因进行了研究。结果表明,供试土壤pH值较原土样下降了1．0个单位。除石灰性土壤外,其它中酸性土壤交换性锰明显增加,造成油菜对锰吸收过量,同时由于吸收过程中锰铁拮抗作用的存在,植株在土壤锰毒发生后吸收的铁量下降,使体内锰铁比上升。     

Ecotoxicity assessment of soil irrigated with domestic wastewater using different extractions

The toxicity of soil irrigated with treated domestic wastewater (site A) and untreated gray wastewater (site B) were investigated. Soil extracts were prepared using distilled water, acid solvent (0.1 mol·L^-1 HCl), and organic solvent (acetone:petroleum ether:cyclohexane= 1:1:1) to understand the type of pollutants responsible for the ecotoxicity associated with wastewater irrigation. The soil toxicity was assessed using a luminescence inhibition assay with Vibrio fischeri for acute toxicity, a micronucleus assay with Vicia faba root tips and a single cell gel electrophoresis assay of mice lymphocytes for genotoxicity. The physicochemical properties and the heavy metal (HM) contents of the irrigated soil were also analyzed. The results indicated that the wastewater irrigation at site A had no effects on the soil properties. With the exception of Pb, Zn, Fe, and Mn, the accumulation of HMs (Cu, Ni, and Cr) occurred. However, the irrigation at site A did not result in obvious acute toxicity or genotoxicity in the soil. The soil properties changed greatly, and HMs (Cu, Ni, and Cr) accumulated in site B. There were significant increases in the acute toxic and genotoxic effects in the soils from site B. The ecotoxicity in site B came primarily from organic-extractable pollutants.     

Mineral status of soils and forage in the Mole National Park,Ghana and implications for wildlife nutrition

Geochemical mapping of soils and selected plant species has been carried out in the Mole National Park, Ghana. The distribution of the essential nutrients: cobalt, copper and manganese is largely controlled by bedrock geology, while the geochemical dispersion of Ca, I, Fe, Mg, Mo, P, K, Se, Na and Zn has been modified by soil and hydromorphic processes. From selective extraction experiments, Fe, Mn and Co are found to be largely fixed in the soil mineral fraction. Larger proportions of Cu, I, Mo, Se and Zn are EDTA extractable and have a high chelation potential.Cobalt, Cu and Mn were preferentially concentrated in grass species while molybdenum and selenium are concentrated in browse plants. Copper uptake is antagonistic to Fe, Mo and Zn accumulation in all plant and grass samples. Similarly, Se and Mn appear antagonistic and Fe uptake is antagonistic to Co, Cu, Mn, Mo and Zn.The low concentration of P points to a potential dietary deficiency of this element throughout the park. Cobalt deficiency may also occur due to a love extractability of these elements in the soils and low concentration in plants. However, the lack of data on the elemental requirements of wildlife allows only tentative conclusions to be drawn.     

The Buffer Capacity of Calcareous Soils in Gansu Province of China

In this study, we added increments of acid and base to three calcareous soils from the eastern, middle and western parts of Gansu Province (China) and to three treated soils to remove calcium carbonate, organic matter and both carbonate and organic matter, respectively. the titration curves were measured and the magnitudes of buffer capacities as a function of pH were computed. It was found that the buffer capacity of calcareous soil is mainly attributed to calcium carbonate, as expected from the chemical composition of calcareous soil, while cation exchange system, silicate buffer system and organic matter play a minor role. the results clearly show that these soils of Gansu Province will not become a problem in the near future from the entrance of H⁺ into these soils.     

Nuclear magnetic resonance studies of interactions between organic pollutants and soil components,a review

This article presents a short overview of selected recent papers using nuclear magnetic resonance (NMR) to investigate interactions between organic pollutants and soil components such as organic matter, clays, whole soils, and sediments. First, we describe solid state cross polarisation magic angle spinning (CP-MAS) experiments as the main tools to investigate covalent bonds. Second, we report NMR approaches allowing us to assess molecule mobility and to characterise non-covalent interactions. Those approaches include correlations between K _oc values and soil organic matter functions determined by CP-MAS, ²H NMR fingerprints, relaxation time measurements, ¹⁹F and ¹H high resolution (HR)-MAS experiments.     

湖北省土壤有效硅含量分布

在全省主要土壤上布点，取土壤样品529个．全省土壤有效硅（SiO2）平均含量为202.6mg／kg，含量变化范围为15．7－725.5mg／kg，低于缺硅临界值（＜95mg／kg）的样点占总样点的38.2％．其土壤有效硅平均含量高的有：黄褐土（471．3mg／kg）、石灰土（377.3mg／kg）和灰潮土（332.7mg／kg）；平均含量中等的有：紫色土（189、5mg／kg）、水稻土（174.7mg／kg）、潮土（110.7mg／kg）、黄棕壤（106.0mg／kg）；平均含量低于缺硅临界值的有红壤（89.1mg／kg）和黄壤（41.4mg／kg）土壤有效硅含量对土壤母质有依赖关系．土壤pH值及水稻上不同水型对土壤有效硅含量也有影响，土壤有效硅含量与土壤有效磷、铁、锰存在着相关关系．     

Chemical composition of plant silica phytoliths

Silica phytoliths are a subgroup of biogenic opal. Silica phytoliths are formed in many plant species and remain preserved in soil and sediments after plant decay. The chemical composition of fossil phytoliths may reveal ancient plant taxa, soil composition and climate. However, actually detailed knowledge on silica phytolith composition is scarce. Here we present result of instrumental neutron activation analysis of barley awns, stems and leaves, and barley phytoliths. The elements of interest were Na, Mg, Al, Si, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Zn, As, Br, Rb, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Dy, Yb, Hf, Ta, W, Th, and U. We compared three phytolith extraction methods: dry ashing, acid digestion, and acid digestion followed by incineration. We found that sole acid digestion is inefficient to remove organic matter. By contrast both dry ashing and acid digestion followed by incineration are suitable for phytolith analysis. Comparison of phytoliths with their source plant material shows that phytoliths are enriched in terrigenous elements such as Al, Sc, Ti, V, Cs, Fe, rare earth elements, and depleted in the major inorganic constituents of plants such as K, Ca, Mg, Mn, Cl and Br.     

Level,pattern, and risk assessment of the selected soil trace metals in the calcareous-cultivated Vertisols

Dynamics and distribution pattern of trace metals in agricultural lands are an increasing concern due to potential risks to the environment and human health. To ascertain more knowledge of this aspect, the fractions of total and available Fe, Mn, Zn, Cu, and Cd belonging to Vertisols under intensive cultivation and adjoining uncultivated soils were investigated. The order of abundance of metals in both cultivated and uncultivated soils was Fe?>?Mn?>?Cu?>?Zn?>?Cd and Fe?>?Mn?>?Zn?>?Cu?>?Cd for both available and total fraction, respectively. A relative enrichment was observed in the value of diethylene-triamine pentaacetic acid-extractable Fe (1.2–201%), Mn (2–31%), Cu (1–40%), and Cd (21–45%) as well as total fraction of Zn (3–17%), Cu (12–32%), and Cd (42–108%) after intensive cropping, which can be contributed to repeated application of agrochemical inputs and manure over long time. The values of RI (potential ecological risk) showed that cultivation caused a low potential ecological risk (33.3% of the soil samples) to moderate potential ecological risk (66.7% of the soil samples) in the study region and that cadmium made up 88%, on average, of the RI value.     

Sequence of the main geochemical controls on the Cu and Zn fractions in the Yangtze River estuarine sediments

Metal speciation can provide sufficient information for environmental and geochemical researches. In this study, based on the speciation determination of Cu and Zn in the Yangtze Estuary sediments, roles of eight geochemical controls (i.e., total organic carbon (TOC), clay, Fe/Mn in five chemical fractions and salinity) are fully investigated and sequenced with correlation analysis (CA) and principal components analysis (PCA). Results show that TOC, clay and Fe/Mn oxides are key geochemical factors affecting the chemical speciation distributions of Cu and Zn in sediments, while the role of salinity appears to be more indirect effect. The influencing sequence generally follows the order: TOC>clay>Mn oxides>Fe oxides>salinity. Among the different fractions of Fe/Mn oxides, residual and total Fe content, and exchangeable and carbonate Mn exert the greatest influences, while exchangeable Fe and residual Mn show the poorest influences.     

Peak assignments for phosphorus-31 nuclear magnetic resonance spectroscopy in pH range 5–13 and their application in environmental samples

Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy has become popular for the characterization of P species in environmental samples. However, these are commonly made alkaline (pH?>?13) to facilitate sample comparison and ease peak identification, but this may cause hydrolysis of some compounds. This study examined the chemical shift of known P compounds and supplemented this with published data to determine the viability of examining samples at their native pH, thereby minimizing sample disturbance. A ³¹P NMR pH titration of known P compounds resulted in chemical shifts ranging from about ?22 to 8 ppm in the pH range 5–13. Categorization and calculation of chemical shifts for over 100 naturally occurring compounds indicated that good distinction between orthophosphate diesters, orthophosphate monoesters, nucleotides, phosphonates, and phosphagens was best at ≥pH 7, but unlikely below this pH. Analysis of several water extracts of soil and dung, overland flow samples, and lake water indicated a wide variety of well-defined peaks that were assigned to orthophosphate, orthophosphate monoesters, orthophosphate diesters, pyrophosphate, polyphosphate, or phosphonates. Changing the sample pH to >13 caused many species (such as phosphonates, orthophosphate diesters, and polyphosphates) to decrease either by hydrolysis or precipitation. Hence, it is recommended that samples be analysed at their native pH but, if poorly resolved, should have their pH raised to ≥7.