Toxicity of root-applied sulphite in Zea mays

Zea mays was grown in nutrient solution with different concentrations of sulphite and sulphate (0, 5, and 10 mM) at pH 5 or 7, with or without aeration, for five days. Sulphite injured the plants, especially at low pH. Lack of aeration increased the sulphite injury of the plants at the high pH. in the aerated solutions, sulphite concentrations approached zero after five hours, while the unaerated solutions still contained sulphite after four days. Very little sulphite was found in the plants. The results indicate that the toxicity to the plants of the different chemical species of the sulphite in the solution decreases in the following order: SO₂ (aq) > HSO₃ ^– > SO₃ ^2–.     

Inorganic element uptake by barley from soil supplemented with flue gas desulphurization waste and fly ash

To evaluate the influence of waste products from coal- and oil-fired power plants on the inorganic element content of plants, barley was grown in pots each with 22 kg of sandy loam supplied with increasing amounts of six waste products. The plants were harvested at maturity and analysed for a number of inorganic elements. The salinity of the soil was the limiting factor for the amount added in terms of plant growth. Concerning the quality of the plants as fodder, addition of the waste to the soil at levels of about 0.5% by weight increased the Se concentration of the barley from a level deficient for animals to that approaching sufficiency for animals. The increase in Cd from the flue gas desulphurization (FGD) products was deemed undesirable, even though the concentrations following this single addition were far from toxic. All other increases in element concentrations were without any biological significance.Environmental Geochemistry and Health, 1988,10(1), 21–25     

Degradation of diuron by the electro-Fenton process

The degradation of the herbicide diuron has been undertaken by electrochemical advanced oxidation in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Hydroxyl radicals degrade diuron in less than 10 min. Kinetic results evidence a pseudo-first-order degradation, with a rate constant of reaction between diuron and hydroxyl radicals of 4.8x10⁹ M^–1 s^–1. Several degradation products were identified by chromatography-mass spectrometry (LC-MS). The mineralization degree of a 1.7x10^–4 M diuron solution reached 93% at 1,000 coulombs.     

Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton

Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l ^–1 Fe²⁺ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO₃^– and NH₄⁺ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole.     

Photocatalytic oxidation of humic substances with TiO<Subscript>2</Subscript>-coated glass micro-spheres

The photocatalytic oxidation of humic substances in aqueous solutions and natural waters with TiO₂ attached to buoyant, hollow glass micro-spheres was studied. A maximum oxidation efficiency of 3.6 mg W^–1 h^–1 was achieved in neutral or alkaline media at a plane surface concentration of the catalyst attached to the micro-spheres of 25 g m^–2. Proceeding by different mechanisms in acidic and alkaline media, the photocatalytic oxidation efficiency did not benefit from an excessive presence of hydroxyl radical promoters, hydrogen peroxide and alkali.     

哒嗪硫磷水解与土壤降解研究

采用室内模拟方法,研究了哒嗪硫磷在东北黑土、江西红壤和南京黄棕壤3种不同类型土壤中的降解特性及pH、温度和表面活性剂（SDS）浓度对水解的影响。结果表明,哒嗪硫磷水解速率随pH值与温度的升高而显著加快,在15℃、pH 5缓冲溶液中水解半衰期为216.56 d,在35℃、pH 9缓冲溶液中半衰期为3.47 d,平均温度效应系数为2.98。SDS能显著抑制哒嗪硫磷水解,且随着浓度的增大抑制作用增强。哒嗪硫磷在3种土壤中的降解速率依次为南京黄棕壤〉东北黑土〉江西红壤,半衰期分别为10.27、78.75、105.00 d,降解速率随土壤pH值的增大而增大。灭菌处理下,哒嗪硫磷在3种土壤中半衰期显著延长,其中在南京黄棕壤中半衰期延长近10倍,哒嗪硫磷在土壤中降解主要为微生物降解。     

Principal Biogeochemical Factors Affecting the Speciation And Transport of Mercury through the terrestrial environment

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH^–, Cl^– and S^– ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)₂, HgCl₂, HgOH⁺, HgS, and Hg⁰ are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH⁺, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl^– concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.     

Catalytic decomposition of hypochlorite ion in petrochemical plant waste water

During the incineration of the chlorinated hydrocarbons originating as the side products in vinyl chloride plant, hypochlorite ion appears as a pollutant in plant waste water. To remove it to the permitted level of 2 mg/l the process of the catalytic oxidation by cobalt (II, III) oxide, followed by sodium sulphite treatment has been chosen. It was shown that the above choice gives satisfactory results. The influence of some parameters such as retention time, effluent pH and temperature versus removal efficiency have been determined.     

Optimum Nitrogen Use and Reduced Nitrogen Loss for Production of Rice and Wheat in the Yangtse Delta Region

A long-term field and lysimeter experiment under different amount of fertilizer-N application was conducted to explore the optimal N application rates for a high productive rice–wheat system and less N leaching loss in the Yangtse Delta region. In this region excessive applications of N fertilizer for the rice–wheat production has resulted in reduced N recovery rates and environment pollution. Initial results of the field experiments showed that the optimal N application rate increased with the yield. On the two major paddy soils (Hydromorphic paddy soil and Gleyed paddy soil) of the region, the optimal N application rate was 225–270 kg N hm^–2 for rice and 180–225 kg N hm^–2 for wheat, separately. This has resulted in the highest number of effective ears and Spikelets per unit area, and hence high yield. Nitrogen leaching in the form of NO ₃ ^– -N occurs mainly in the wheat-growing season and in the ponding and seedling periods of the paddy field. Its concentration in the leachate increased with the N application rate in the lysimeter experiment. When the application rate reached 225 kg N hm^–2, the concentration rose to 5.4–21.3 mgN l^–1 in the leachate during the wheat-growing season. About 60% of the leachate samples determined contained NO ₃ ^– -N beyond the criterion (NO ₃ ^– -N 10 mg l^–1) for N pollution. In the field experiment, when the N application rate was in the range of 270–315 kg hm^–2, the NO ₃ ^– -N concentration in the leachate during the wheat-growing season ranged from 1.9 to 11.0 mg l^–1. About 20% of the leachate samples reached close to, and 10% exceeded, the criterion for N pollution. Long-term accumulation of NO ₃ ^– -N from leaching will no doubt constitute a potential risk of N contamination of the groundwater in the Yangtse Delta Region.     

Long-term geochemical evolution of acidic mine wastes under anaerobic conditions

A nearly 5-year anaerobic incubation experiment was conducted to observe the geochemical evolution of an acidic mine waste. Long-term storage of the mine waste under strict anaerobic conditions caused marked increase in aqueous sulfur, while aqueous iron showed no remarkable change. Co-existing oxidation and reduction of elemental sulfur appeared to play a central role in controlling the evolutionary trends of aqueous sulfur and iron. Addition of organic matter increased the aqueous Fe concentration, possibly due to enhanced iron mobilization by microbial iron reduction and increased iron solubility by forming organically complexed Fe species. Further addition of CaCO₃ resulted in immobilization of aqueous iron and sulfur due to elevated pH and gypsum formation. The chemical behaviors of environmentally significant metals were markedly affected by the added organic matter; Al, Cr, Cu, Ni and Zn tended to be immobilized probably due to elevated pH and complexation with insoluble organic molecules, while As and Pb tended to be mobilized. Jarosite exhibited high stability after nearly 5 years of anaerobic incubation and even under circumneutral pH conditions. Long-term weathering of aluminosilicate through acid attack raised pH, while continuous reaction between the added CaCO₃ and mine waste-borne stored acid decreased pH.     

Influence of fertilizer and sewage sludge compost on yield and heavy metal accumulation by lettuce grown in urban soils

Previous research has demonstrated that many urban soils are enriched in Pb, Cd and Zn. Culture of vegetable crops in these soils could allow transfer of potentially toxic metals to foods. Tanya lettuce (Lactuca sativa L.) was grown in pots of five urban garden soils and one control agricultural soil to assess the effect of urban-soil metal enrichment, and the effect of soil amendments, on heavy metal uptake by garden vegetables. The amendments included NPK fertilizer, limestone, Ca(H₂PO₄)₂, and two rates of limed sewage sludge compost. Soil Cd ranged from 0.08 to 9.6 mg kg^–1; soil Zn from 38 to 3490 mg kg^–1; and soil Pb from 12 to 5210 mg kg^–1. Lettuce yield on the urban garden soils was as great as or greater than that on the control soil. Lettuce Cd, Zn and Pb concentrations increased from 0.65, 23, and 2.2 mg kg^–1 dry matter in the control soil to as high as 3.53, 422 and 37.0 mg kg^–1 on the metal-rich urban garden soils. Adding limestone or limed sewage sludge compost raised soil pH and significantly reduced lettuce Cd and Zn, while phosphate fertilizer lowered soil pH and had little effect on Zn but increased Cd concentration in lettuce. Urban garden soils caused a significant increase in lettuce leaf Pb concentration, especially on the highest Pb soil. Adding NPK fertilizer, phosphate, or sludge compost to two high Pb soils lowered lettuce Pb concentration, but adding limestone generally did not. On normally fertilized soils, Pb uptake by lettuce was not exceptionally high until soil Pb substantially exceeded 500 mg kg^–1. Comparing garden vegetables and soil as potential sources of Pb risk to children, it is clear that the risk is greater through ingestion of soil or dust than through ingestion of garden vegetables grown on the soil. Urban dwellers should obtain soil metal analyses before selecting garden locations to reduce Pb risk to their children.     

Modelling the biochemical oxidation processes in artificial conditions of waste treatment plants

For natural water bodies there are many models of biochemical oxidation of organic pollutants, from simple to complicated ones. For the artificial conditions of waste water treatment plants there are numerous models of oxidation processes too. The authors believe that a better understanding of these processes in nature would be gained if the oxidation processes in more simple artificial conditions were understood.An attempt has been made to explain the variety of types of models of waste treatment in an activated sludge system or a biofilm reactor by the diffusion mechanism of oxidation of single substrates on the one hand, and by superposition of the kinetics of oxidation of single substrates in measurements of the dynamics of oxidation of a complex pollutant on the other hand.The conditions in which zero- and first-order models are valid in the oxidation of single substrates are derived. Respective formulae for rate constants are given. Monod's model is valid in a broader range of substrate concentration variations. An approximate formula for the half-saturation constant is proposed. Satisfactory agreement with experimental data for glucose and ammonia substrates is shown.The formal character of models being used at present is claimed for multicomponent substrates. The accuracy of the calculation is largely governed by the number of model coefficients. Similar results obtained by Monod's and Grau's models, often used in practice, are emphasized.     

Natural and waste materials as metal sorbents in permeable reactive barriers (PRBs)

A range of waste products and natural materials including chitin, fly ash, clay soil, cocoa shell, calcified seaweed and the natural zeolite clinoptilolite were tested in batch experiments to assess their ability to remove metals from a synthetic groundwater containing 10 mg l^–1 Cu, Pb and Zn and 1 mg l^–1 Cd. All had the ability to remove more than 70% of the metals from solution with fly ash being the most efficient, then chitin, clinoptilolite, calcified seaweed, clay soil and cocoa shell. After consideration of geochemical and morphological properties, calcified seaweed and clinoptilolite were shown to have potential as barrier materials. Given current issues with regard to the longevity of zero-valent iron barriers alternative materials could be the key to the future adoption of this remediation technology.     

Effects of the Interactions Between Selenium and Phosphorus on the Growth and Selenium Accumulation in Rice (Oryza Sativa)

The solution culture, paddy soil culture and the simulation experiments in the laboratory were conducted to clarify the interactions between selenium and phosphorus, and its effects on the growth and selenium accumulation in rice. Results revealed that a suitable supply of selenium could promote rice growth and excessive selenium could injure rice plant, causing lower biomass, especially in the roots. The supply of selenite could enhance the selenium contents of rice shoots and roots in solution culture and in soil culture. The selenium concentrations in roots were much higher than those in shoots supplied with the same rates of selenium and phosphorus. The interaction between selenium and phosphorus was evident. When the phosphorus supply increased to meet the needs of plant growth, phosphorus could promote absorption and accumulation of selenium in the shoots. If the phosphorus supply was excessive, phosphorus could inhibit the accumulation of selenium in the shoots at the lower selenite level (2 mol l^–1), but could not at the higher selenite level (10 mol l^–1). With the supply of phosphate increased, the selenium concentrations in the roots decreased significantly at both selenite levels. The presence of phosphate could decrease Se sorption on the soil surface and increase the selenium concentration in the soil solution. The concentrations of selenium in shoots and roots supplied with 0.08 g kg^–1 phosphorus were lower than those with no phosphorus supplied. With the increase of phosphorus added to 0.4 g kg^–1, the selenium concentration in shoots and roots increased. The effect of phosphorus on the concentration was statistically significant at all three selenium levels.     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

Single and Joint Effects of Acetochlor and Urea on Earthworm Esisenia Foelide Populations in Phaiozem

Much attention is paid to soil health and environmental safety. Earthworms are an important indicator of soil ecosystem health and safety. Ecological toxicity of acetochlor and excessive urea, in both their single and joint effects, on earthworm Esisenia foelide was thus studied using the soil-culture method. Acetochlor had an enhanced toxicity from low concentration to high concentration. The mortality of earthworms after a 6-day exposure was changed from 0 to 86.7%, and the weight change rate ranged from 7.86 to –30.43%, when the concentration of acetochlor was increased from 164 to 730 mg kg^–1. Urea expressed its positive and beneficial effects on earthworms when its concentration was lower than 500 mg kg^–1. Strongly toxic effects took place when the concentration of urea was higher than 1000 mg kg^–1. The mortality of earthworms exposed to urea reached 100% when its concentration was more than 1500 mg kg^–1. When the concentration of urea was lower than 500 mg kg^–1, there were antagonistic effects between the two agrochemicals on earthworms; when the concentration of urea was higher than 500 mg kg^–1, joint toxic effects of acetochlor and excessive urea on earthworms were synergic. In any case, excessive urea application is very harmful to the health of soil ecosystems.     

The chemistry of aluminum in the environment

There is increased concern over the effects of elevated concentrations of Al in the environment. Unfortunately, studies of the environmental chemistry and toxicity of Al have been limited by our understanding of the processes regulating the aqueous concentration, speciation and bioavailability of this element.Although Al is the most abundant metallic element in the Earth's crust, it is highly insoluble and generally unavailable to participate in biogeochemical reactions. However, under highly acidic or alkaline conditions, or in the presence of complexing ligands, elevated concentrations may be mobilized to the aquatic environment. Ecologically significant concentrations of Al have been reported in surface waters draining acid-sensitive regions that are receiving elevated inputs of acidic deposition. Acid- sensitive watersheds are characterized by limited release of basic cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and/or retention of strong acid anions (SO₄ ^2–, NO₃ ^–, Cl^–). Under these conditions inputs of strong acids are not completely neutralized, but rather acidic water is exported from the terrestrial environment. It has been hypothesized that acidic deposition to acid-sensitive watersheds mobilizes Al within the mineral soil, causing elevated concentrations in soil solutions and surface waters. As a result of mineral phase solubility constraints, concentrations of aqueous Al increase exponentially with decreases in pH below 6.0.Monomeric Al occurs as a series of complexes in the aqueous environment, including aquo, OH^–, F^–, SO₄ ^2–, HCO₃ ^– and organic species. Of these aquo, OH^–, F^– and organic complexes are the most significant in natural waters.Elevated concentrations of Al are ecologically significant because: 1) Al is an important pH buffer in acidic waters, regulating the lower limit of pH values following acidification by strong acids; 2) through adsorption and coagulation reactions, Al may alter the cycling and availability of important elements like phosphorus, organic carbon and certain trace metals; 3) Al may serve as a coagulant facilitating the removal of light attenuating materials, thereby increasing the clarity and decreasing the thermal stability of lakes; and 4) Al is potentially toxic to organisms. Better understanding of the chemistry and speciation of Al is essential to assess these effects.     

Influence of human-induced disturbance on benthic microbial metabolism in the Pichavaram mangroves,Vellar–Coleroon estuarine complex,India

Large areas of mangroves in India are heavily disturbed by cattle grazing, hypersalinity, and other human-induced impacts. In two disturbed Avicennia marina forests and two undisturbed A. marina and Rhizophora apiculata forests in the Pichavaram mangroves of the Vellar–Coleroon estuarine complex, southeast India, we measured the rates and pathways of microbial decomposition of soil organic matter to determine if human impact is altering biogeochemical activity within these stands. Rates of total carbon oxidation (T_COX) were higher in the undisturbed A. marina forest (mean 199 mol C m^–2 year^–1) than in the two impacted stands (43 and 79 mol C m^–2 year^–1); rates of total carbon oxidation in the R. apiculata forest averaged 75 mol C m^–2 year^–1. Sulphate reduction (range 21–319 mmol S m^–2 day^–1) was the major decomposition pathway (65–85% of T_COX), except at the most disturbed forest (30% of T_COX). Rates of sulphate reduction at all sites peaked in sub-surface soils to a depth of about 1 m, leading to little carbon burial (3–5% of total C input). There was some evidence of measurable iron and manganese reduction in association with tree roots. Rates of microbial activity were rapid in comparison with rates measured in other mangrove soils, reflecting high rates of phytoplankton production and organic matter retention in this lagoon. Human-induced disturbance creates a sharp zonation of dry, hypersaline soil overlying less saline, wetter soil, suppressing surface microbial and root growth. We conclude that this vertical alteration of soil characteristics and biogeochemistry shifts the cycling of nutrients between trees and microbes to a disequilibrium state, partly explaining why mangroves are stunted in these declining forests.Communicated by G. F. Humphrey, Sydney     

柠檬酸对土壤养分的活化及对作物吸收Fe、P的影响

土壤pH值是影响石灰性土壤Fe、Zn、Mn等微量元素有效性的重要因素，利用土壤培养法，研究了不同浓度柠檬酸溶液对石灰性土壤的pH值以及对P、Fe、Mn、Zn等元素的活化效应。结果表明，浓度高于0．001mol／L的柠檬酸溶液培养土壤，可降低土壤pH值，增加土壤有效P、Fe、Mn、Zn等元素的质量分数。培养24h后，P、Fe、Mn、Zn等有效养分质量分数最高，随着培养时间的延长，有效养分的质量分数下降，活化效果减弱，土壤表现出一定的钝化效应。利用盆栽模拟滴灌施肥条件，柠檬酸溶液处理可显著促进花生、菜豆植株的生长，叶片SPAD读数增加，并提高植株对P、Fe元素的吸收量，因此滴灌施肥条件下，可考虑使用柠檬酸增加石灰性土壤根区微量元素的有效性。     

Sequential extraction of copper from soils and relationships with copper in maize

We studied copper uptake by maize grown on soils that have been contaminated with CuSO₄. In soil the total copper level ranged from 24 to 135 mg kg^–1. The copper distribution in soil fractions was assessed by sequential extraction, showing that anthropogenic copper is mainly concentrated in oxides fractions. The copper concentration of maize at the maturity stage reached values from 36.3 to 65.9 mg kg^–1 compared to copper levels usually found in non-contaminated crops (5–30 mg kg^–1). Here we demonstrate that copper can be accumulated by maize and that copper concentration in maize can be predicted by equations including copper concentration of soil fractions.