Trace Element Concentrations in Saltmarsh Soils Strongly Affected by Wastes from Metal Sulphide Mining Areas

Soil and water samples were analysed for trace metals and As in two watercourses and 14 sampling plots in a salt marsh polluted by mine wastes in SE Spain. Groundwater levels, soil pH and Eh were measured ‘in situ’ for a 12-month period in each sampling plot, and total calcium carbonate was also determined. Low concentrations of soluble metals (maximum Mn 1.089 mg L^?1 and maximum Zn 0.553 mg L^?1) were found in the watercourses. However, total metal contents were extremely high in the soils of a zone of the salt marsh (maximum 1,933 mg kg^?1 of Mn, 62,280 mg kg^?1 of Zn, 16,845 mg kg^?1 of Pb, 77 mg kg^?1 of Cd, 418 mg kg^?1 of Cu and 725 mg kg^?1 of As), and soluble metals in the pore water reached 38.7 mg L^?1 for Zn, 3.15 mg L^?1 for Pb, 48.0 mg L^?1 for Mn, 0.61 mg L^?1 for Cd and 0.29 mg L^?1 for As. Variable concentrations with depth indicate a possible re-mobilisation of the metals, which could be related to spatial and temporal variations of water table level, pH and Eh and to the presence of calcium carbonate. A tendency for the Eh to decrease in the warmest months and to increase in the coldest ones was found, especially, in plots that received water with a high content of dissolved organic carbon. Hence, the existence of nutrient effluent-enriched water may modify the physical–chemical conditions of the soil–water system and influence metal mobility.     

Retention of Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.     

Toxicity and binding of copper,zinc, and cadmium by the blue-green alga,Chroococcus paris

The toxic effects and accumulation of the heavy metals, Cd, Cu, and Zn by the sheath forming blue-green alga Chroococcus paris were investigated. All three of the metals were bound rapidly. Approximately 90% of the total amount of the added metal was bound within 1 min. Further significant binding occurred at a slower rate. The maximum metal binding capacity, as determined by filtration studies, was determined to be 53, 120, and 65 mg g^?1 dry algal weight for Cd, Cu, and Zn, respectively. Binding curves for the metals followed the Langmuir adsorption isotherm model. The amount of metal bound increased with increasing pH. Metal binding increased significantly when pH was increased from 4 to 7. Nearly all of the metal was found to be rapidly EDTA extractable. Metals were found to be increasingly toxic to growing cultures in the order, Zn, Cd, and Cu. All of the metals studied exhibited toxic effects at concentrations greater than 1.0 mg L^?1. The lowest concentrations used which showed detectable toxicity were 0.1 mg L^?1 for Cu and >0.4 mg L^?1 for Cd and Zn.     

Effects of Broiler Litter Management Practices on Phosphorus,Copper, Zinc,Manganese, and Arsenic Concentrations in Maryland Coastal Plain Soils

Abstract

The objective of this research was to assess the long‐term effects of broiler litter applications on soil phosphorus (P), copper (Cu), zinc (Zn), manganese (Mn), and arsenic (As) concentrations in Chesapeake Bay watershed Coastal Plain soils. Litter and soil samples were collected from 10 farms with more than 40 years of broiler production and from wooded sites adjacent to fields and were analyzed for P and metal contents. Averaged over farms, total P and metal concentrations in the litter were 12.8 g kg^?1 P and 332, 350, 334, and 2.93 mg kg^?1 Cu, Zn, Mn, and As, respectively. Surface (0–15 cm) soil pH values were greater than (5.7–6.4) the 0‐ to 15‐cm depth at wooded sites (3.5–4.3). Surface soil Bray 1 P values (149–796 mg kg^?1) in amended fields were greater than wooded sites (4.4–17 mg kg^?1). The 1N nitric acid (HNO₃)–extractable metal concentrations were higher in amended soils than in wooded areas and were 7.7–32, 5.7–26, 12.3–71, and 0.6–3.0 mg kg^?1 for Cu, Zn, Mn, and As, respectively, compared to 0.76–14, 4.6–22, 1.6–70, and 0.14–0.59 mg kg^?1 for the same metals, respectively, in wooded areas. Results from this study demonstrated that long‐term broiler litter applications have altered the chemical properties of the Coastal Plain soils of the Maryland Eastern Shore. Metal concentrations were low in the surface layer of amended fields and typically decreased with depth. Phosphorus additions rather than metals are most likely to contribute to the degradation of the Chesapeake Bay watershed.     

EFFECT OF LANTHANUM ON RICE PRODUCTION,NUTRIENT UPTAKE,AND DISTRIBUTION

ABSTRACT

Split root solution culture experiments were conducted to study the effects of the rare earth element lanthanum (La) on rice (Oryza sativa) growth, nutrient uptake and distribution. Results showed that low concentrations of La could promote rice growth including yield (0.05 mg L^?1 to 1.5 mg L^?1), dry root weight (0.05 mg L^?1 to 0.75 mg L^?1) and grain numbers (0.05 mg L^?1 to 6 mg L^?1). High concentrations depressed grain formation (9 mg L^?1 to 30 mg L^?1) and root elongation (1.5 mg L^?1 to 30 mg L^?1). No significant influence on straw dry weight was found over the whole concentration range except for the 0.05 mg L^?1 treatment. In the pot and field experiments, the addition of La had no significant influence on rice growth.Lanthanum had variable influence on nutrient uptake in different parts of rice. Low concentrations (0.05 mg L^?1 to 0.75 mg L^?1) increased the root copper (Cu), iron (Fe), and magnesium (Mg), and grain Cu, calcium (Ca), phosphorus (P), manganese (Mn), and Mg uptake. High concentrations (9 to 30 mg L^?1) decreased the grain Ca, zinc (Zn), P, Mn, Fe and Mg, and straw Ca, Mn, and Mg uptake. With increasing La concentration, root Zn, P, Mn, Cu, and Ca concentrations increased, and grain Ca and Fe, and straw Mn, Mg, and Ca concentrations decreased. Possible reasons are discussed for the differences between the effects of La in nutrient solutions and in pot and field experiments.     

Behavior of Metals Under Different Seasonal Conditions: Effects on the Quality of a Mexico–USA Border River

Spatial and seasonal mobilization trends of metals in surface water were evaluated in the US–Mexico San Pedro River (SPR). Water samples were collected at five sampling stations for the analysis of dissolved oxygen, pH, electric conductivity, sulfates, and metals (Cd, Cu, Fe, Mn, Pb, and Zn). Quality of the water was characterized through Ecological Criteria of Water Quality (ECWQ) established in Mexico and Water Quality Criteria (Environmental Protection Agency (EPA)). High total metal concentrations were detected as follows: Fe?>?Cu?>?Mn?>?Zn?>?Pb?>?Cd. Metal concentrations were slightly higher in dry season than in rainy season: Cd (below detection limit (BDL)–0.21 mg L^?1), Cu (BDL–13 mg L^?1), Fe (0.16–345 mg L^?1), Mn (0.12–52 mg L^?1), Pb (BDL–0.48 mg L^?1), and Zn (0.03–17.8 mg L^?1). Low pH and dissolved oxygen values as well as high sulfate content were detected in both seasons. High values of metals (Cd, Cu, Fe, Mn, Pb, Zn) were detected at station E1 representing pollution source, as well as at stations E2 (Cd, Cu, Fe, Mn), E3 (Fe, Mn, Pb), and E4 and E5 (Fe, Mn). Detected concentrations exceeded maximum permissible established in ECWQ and Water Quality Criteria (EPA). Efflorescence salts on sediments in the dry season could increase levels of metals in water column. This study provides valuable information on the potential mobility of metals in surface water of SPR located in an arid environment where transport processes are strongly linked to climate. The information derived from this study should help the regional and national authorities to address present environmental regulations.     

Valuable Metal Recovery During the Bioremediation of Acidic Mine Drainage Using Sulfate Reducing Straw Bioremediation System

Recovery of valuable metals from acidic mine drainage (AMD) during bioremediation using straw bioremediation system was investigated, with observation of efficient metal recovery. The recovery loading rates of Cu and Zn were 46.19?±?6.13 and 43.86?±?6.76?mg?m^?3?h^?1, respectively. More than 97.0% of Cu and more than 87.0% of Zn were recovered from AMD during bioremediation. The recovery loading rate of Cu increased by 4.54?mg?m^?3?h^?1 for each 1?mg?L^?1 increase in influent concentration while that of Zn increased by 4.08?mg?m^?3?h^?1. Heavy metal toxic effect on the metal recovery in the straw bioremediation system could be neglected in most cases. Low pH could severely decrease recovery rate of Zn, while it had no influence on that of Cu. The recovery loading rate of Zn decreased by almost 70% when the influent pH decreased from 7.0 to 3.0. Cu could be recovered efficiently even at a short hydraulic residence time (HRT) of 18?h, while Zn could only be efficiently recovered at a relatively long HRT of 80?h, indicating that selective metal recovery might be achieved with relatively short HRT and bioreactor process optimization. These findings suggested the feasibility of using sulfate-reducing straw bioremediation system to recover valuable metals during bioremediation of AMD.     

Enhanced Heavy Metal Phytoextraction from Marine Dredged Sediments Comparing Conventional Chelating Agents (Citric Acid and EDTA) with Humic Substances

Metal (Cu, Mn, Ni, Zn, Fe) concentrations in marine sediment and zooplankton were investigated in Izmir Bay of the Eastern Aegean Sea, Turkey. The study aimed to assess the levels of metal in different environmental compartments of the Izmir Bay. Metal concentrations in the sediment (dry weight) ranged between 4.26–70.8 μg g^?1 for Cu, 233–923 μg g^?1 for Mn, 14.9–127 μg g^?1 for Ni, 25.6–295 μg g^?1 for Zn, 12,404–76,899 μg g^?1 for Fe and 38,226–91,532 μg g^?1 for Al in the Izmir Bay. Maximum metal concentrations in zooplankton were observed during summer season in the inner bay. Significant relationships existed between the concentrations of certain metals (Al, Fe, Mn and Ni) in sediment, suggesting similar sources and/or similar geochemical processes controlling such metals. Higher concentrations of Cu, Zn and percent organic matter contents were found in the middle-inner bays sediments. Based on the correlation matrix obtained for metal data, organic matter was found to be the dominant factor controlling Cu and Zn distributions in the sediment. In general, mean Cu and Zn levels in the bay were above background concentrations in Mediterranean sediments. Zooplankton metal concentrations were similar to sediment distributions.     

Toxic Metal Removal from Polluted Soil by Acid Extraction

Sulfuric acid leaching is a promising technique to extract toxic metals from polluted soils. The objective of this study was to define the optimum sulfuric acid leaching conditions for decontamination of the fine particle fraction (<125???m) of an industrial soil polluted by Cd (16.8?mg?kg^?1), Cu (3,350?mg?kg^?1), Pb (631?mg?kg^?1) and Zn (3,010?mg?kg^?1). Batch leaching tests in Erlenmeyer shake flasks showed that a soil pulp pH between 1.5 and 2.0 using a solid concentration (SC) ranging from 5 to 20?% is adequate to efficiently solubilize toxic metals. Leaching tests performed at different temperatures (20, 40, 60 and 80?°C) also revealed that it is not beneficial to heat the soil suspension during the leaching treatment. The application in a 1-L stirred tank reactor of five consecutive 1-h leaching steps at 10?% SC and ambient temperature, followed by three water washings steps resulted in the following metal extraction yields: 30?% As, 90?% Cd, 43?% Co, 7?% Cr, 88?% Cu, 75?% Mn, 26?% Ni, 18?% Pb and 86?% Zn. The decontaminated soil conformed to Quebec norms for commercial and industrial use of soil.     

Interactive Effects of Lanthanum and Cadmium on Plant Growth and Mineral Element Uptake in Crisped-Leaf Mustard Under Hydroponic Conditions

Plant growth and mineral element accumulation in Brassica juncea var. crispifolia (crisped-leaf mustard) under exposure to lanthanum (La) and cadmium (Cd) were studied by employing a hydroponic experiment with a complete two-factorial design. Four levels of La (0.05–5.0 mg L^?1) and two levels of Cd (1.0 and 10.0 mg L^?1) were used in this experiment. Lanthanum did not improve plant growth in this experiment. Addition of La (≥ 1.0 mg L^?1) or Cd (≥ 10 mg L^?1) to the solution inhibited root elongation. Lanthanum treatments reduced accumulations of iron (Fe), manganese (Mn), and zinc (Zn) in roots, and Mn in shoots. Lanthanum at ≥ 1.0 mg L^?1 limited the Cd translocation from roots to shoots and thus decreased the accumulation of Cd in shoots. Cadmium had no influence on La accumulations in roots, but inhibited the accumulation of La in shoots. The study results suggest that applications of rare earth elements in vegetables would be potentially risky to human health.     

Toxicity of heavy metals (Zn,Cu, Cd,Pb) to vascular plants

The literature on heavy metal toxicity to vascular plants is reviewed. Special attention is given to forest plant species, especially trees, and effects at low metal concentrations, including growth, physiological, biochemical and cytological responses. Interactions between the metals in toxicity are considered and the role of mycorrhizal infection as well. Of the metals reviewed, Zn is the least toxic. Generally plant growth is affected at 1000 μg Zn L^?1 or more in a nutrient solution, though 100 to 200 µg L^?1 may give cytological disorders. At concentrations of 100 to 200 μg L^?1, Cu and Cd disturb metabolic processes and growth, whereas the phytotoxicity of Pb generally is lower. Although a great variation between plant species, critical leaf tissue concentrations affecting growth in most species being 200 to 300 μg Zn g^?1 dry weight, 15 to 20 μg Cu g^?1 and 8–12 μg Cd g^?1. With our present knowledge it is difficult to propose a limit for toxic concentrations of Zn, Cu, Cd and Pb in soils. Besides time of exposure, the degree of toxicity is influenced by biological availability of the metals and interactions with other metals in the soil, nutritional status, age and mycorrhizal infection of the plant.     

Metal concentrations in the ground water of the Ouachita Mountains,Arkansas, U.S.A.

Ninety-one ground water samples (predominantly from springs) in two mineralized areas of the Ouachita Mountains in west-central Arkansas, were analyzed for Fe, Mn, Zn, Cu, Co, Ni, Pb, Hg, Sb, Sr, Ba, Ca, and Li. These areas contain Mn, barite, strontianite, cinnabar, stibnite and scattered Pb-Zn mineralization, Cumulative frequency curves were used to determine the threshold and anomalous concentrations for each element in the two areas. These values were, in general, higher in the ground water from the more mineralized area for several of the base metals, but most notably for Mn and Fe, the principal metals in the Mn oxide minerals. The United States Environmental Protection Agency (EPA, 1976) criteria for Fe (300 μg L ^?1) and Mn (50 μg L^?1) in drinking water were exceeded, respectively, in 34% and 30% of the springs in Area I, and 13% and 23% in Area II. One spring exceeded the EPA Hg criterion (2 μg L^?1) and 3 springs exceeded the 50 μg L^?1 criterion for Pb. In spite of the large number of anomalous Ba concentrations, the highest concentration of Ba was 930 μg L^?1 (EPA criterion 1000 μg L ^?1).     

Surface loading effect on Cd and Zn sorption by kaolinite and montmorillonite from low concentration solutions

Studies of Cd and Zn sorption using Na-saturated kaolinite and montmorillonite, and low metal solution concentrations similar to those found in the environment, showed that metal sorption affinity (measured by K _d values) decreased markedly with increasing surface metal loading for both layer silicates. For equilibrium solution concentrations <0.1 μmol L^?1 for Cd, and < 1 μmol L^?1 for Zn, both metals were sorbed with greater affinity by kaolinite than montmorillonite. These results were probably due to the higher proportion of weakly acidic edge sites present on kaolinite surfaces. In the case of Zn there was an affinity reversal for equilibrium solution concentrations > 1 μmol L^?1, which was attributed to the permanent charge sites of montmorillonite. Cadmium ions were sorbed, by kaolinite, with greater affinity than Zn for equilibrium solution concentrations between 0.3 to 1.5 μmol L^?1. This result was attributed to retention of these metal ions through electrostatic attraction by permanent charge sites present on the kaolinite used in this work. According of these results it seems that metal sorption by these layer silicates involves predominantly edge weak acid sites at lower surface coverages (higher affinity sites), and permanent charge sites at higher metal coverages (lower affinity sites). It was concluded that Cd and Zn sorption by those two layer silicates is greatly influenced by surface metal coverage, and results cannot be extrapolated from low to high surface coverages, and viceversa.     

Partitioning of Trace Metals in Suspended Sediments from Huanghe and Changjiang Rivers in Eastern China

Assessing metal contamination of sediments requires knowledge of the geochemical partitioning of trace metals at the sediment-water interface. Under controlled laboratory conditions, sequential extraction was conducted to determine the associations of metals (Cd, Cr, and Zn) and radiotracers (¹⁰⁹Cd, ⁵¹Cr, and ⁶⁵Zn) with various geochemical phases and the different partitioning and mobility of metals for two types of surface sediments collected from the Huanghe and Changjiang Rivers in Eastern China. The residual phase was the major phase for stable metal binding, indicating that these sediments had little subjection to recent anthropogenic influences. Fe–Mn oxides were the next important binding phases for metals. The partitioning of metals in various geochemical phases as a function of the duration of the radiolabeling was also examined. Trace metals transferred among the different geochemical phases over the 30 days radiolabeling period, particularly between the carbonate and Fe–Mn oxides phases. The freshwater-sediment distribution coefficients (K _d) of three metals were investigated in batch experiments using the radiotracer technique. The decreasing K _d with increasing metal concentration(from 0.5 to 200 μg L^-1) may be explained by competitive adsorption. The metal K _d in sediments from the Changjiang River was greater than those from the Huanghe River, presumably because of the higher Fe/Mn and organic carbon contents in Changjiang River sediment. The K _d decreased with increasing total suspended solid load from 3 to 500 mg L^-1, and was Cr > Zn > Cd. For Cd and Zn, increasing the pH from 5 to 8 resulted in an increase in K _d due to the reduced H⁺ competition and increasing sorptionpotential. However, the K _d for Cr in the sediments from both rivers showed no relationship with pH, presumably becauseof the complexity of the Cr species and environmental behavior.     

Efficiency of GAC for Treatment of Leachate from Soil Washing Process

Granular activated carbon (GAC), granular activated alumina (GAA) and a ferric chloride solution (FCS) were tested for the treatment of leachate contaminated by heavy metals. The leachate was collected following the remedation of soils using weak organic acids and/or their salts, EDTA and DTPA. Only GAC was found to effectively remove heavy metals (Cd, Cu, Cr, Hg, Mn, Pb and Zn as chelates) from the leachate. At optimum pH ranging from 5.4 to 6.9, 97% of Hg was removed while at optimum pH ranging from 6.9 to 7.7, 78 to 96% of Cd, Cu, Mn, Pb and Zn were removed. Some 77% of the Cr was removed at optimum pH of 5.4. Adsorption rate constant and Langmuir adsorption capacity of GAC were found to be 0.01 min^?1 and 19 mg metal chelate g^?1 of GAC, respectively. Freundlich constants, k and n were found to be 21 mg g^?1 and 2.778, respectively. The brown color of the leachate turned colorless after GAC treatment.

     

An improved selective extraction method for Mn oxides and occluded metals with emphasis on applicability to Andisols

Abstract

It has been showed that Chao’s method [extraction with 0.1 mol L^?1 hydroxylamine hydrochloride (NH₂OH-HCl) at pH 2.0 for 30 min], which is commonly used to extract manganese (Mn) oxides and occluded heavy metals from soil samples, is not suitable for Andisols because of low solubility, and thus low extractability, of Mn oxides in such soils. Therefore, a new method is evaluated here, for extracting Mn oxides and occluded heavy metals from Andisols, Entisols and Inceptisols. The method has three steps: (1) reduction of Mn oxides with 0.01 mol L^?1 NH₂OH-HCl (pH 5.0) for 16 h, (2) recovery of re-adsorbed metals by short-time extraction with 0.5 mol L^?1 ammonium chloride in 0.02 mol L^?1 hydrochloric acid, and (3) washing with ultrapure water. This method achieves a higher rate of extraction of Mn oxides than does Chao’s method, especially from Andisol samples. Standard addition experiments showed that both the new method and Chao’s method can successfully extract released cadmium (Cd), cobalt (Co), nickel (Ni) and zinc (Zn) from Mn oxides with little re-adsorption. The selectivity of Mn oxide extraction by the new method, indicated by the rate of extraction of iron (Fe) oxides and the aluminum (Al)/Mn and silicon (Si)/Mn extraction ratios, is comparable to that of Chao’s method. Thus, the new method should be useful for extracting Mn oxides and occluded Cd, Co, Ni, and Zn from soil samples. Moreover, because the new method achieved nearly complete extraction of NH₂OH-HCl reactive Mn oxides even from Andisol samples, the method is more applicable to Andisol samples than Chao’s method.     

Heavy metal pollutant tolerance of Azolla Pinnata

The effects of Hg, As, Pb, Cu, Cd, and Cr (1, 2, and 5 mg L^?1 each) on Azolla pinnata R. Br. were analyzed. The treatments (2 and 5 mg L^?1) of the heavy metal pollutants decreased Hill activity, chlorophyll, protein and dry wt, and increased tissue permeability over control values. The effects were most pronounced with the treatment of 5 mg L^?1. The harmful effects of the metals were, in general, found by the treatments in the order: Cd 〉 Hg 〉 Cu 〉 As 〉 Pb 〉 Cr. There was no significant change in these parameters at 1 mg L^?1 of the metals over control. Thus Azolla pinnata shows tolerance to the heavy metals tested up to 1 mg L^?1 each.     

Mobility of Cd and Zn in polluted and unpolluted Spodosols

Leaching of Cd and Zn in polluted acid, well‐drained soils is a critical pathway for groundwater pollution. Models predicting future groundwater contamination with these metals have rarely been validated at the field scale. Spodosol profiles (pH 3.2–4.5) were sampled in an unpolluted (reference) field and in a field contaminated with Cd and Zn through atmospheric deposition near a zinc smelter. Average metal concentrations in the upper horizons were 0.2 mg Cd kg^?1 and 9 mg Zn kg^?1 in the unpolluted field, and 0.8 mg Cd kg^?1 and 71 mg Zn kg^?1 in the contaminated field. Isotopic dilution was used to measure the labile concentration of Cd and Zn, and the metal transport was modelled using measured sorption parameters that describe the distribution between the labile metal pool (instead of the total metal pool) and the solution phase obtained by centrifugation. Solutions were also collected by wick samplers in two polluted and one unpolluted profile at a depth of 70 cm. Concentrations in these solutions were in the order of 15 µg Cd litre^?1 and 0.8 mg Zn litre^?1 for the polluted profiles, and 1 µg Cd litre^?1 and 0.04 mg Zn litre^?1 for the unpolluted profile. The concentrations in these solutions agreed well with those in soil solutions obtained by centrifugation, which supported the use of the local equilibrium assumption (LEA). Present‐day Cd profiles in the polluted field were calculated with the LEA, based on the emission history of the nearby smelter and taking spatial variability into account. Observed and predicted depth profiles agreed reasonably well, but total Cd concentrations in the topsoil were generally underestimated by the model. This may be attributed to the presence of non‐labile Cd in the atmospheric deposition, which was not accounted for in the retrospective modelling. The large concentrations of non‐labile Zn in the topsoil of the polluted field were also indicative that metals in the atmospheric deposition were (partly) in a sparingly soluble form, and that release of these non‐labile metals is a slow process. The presence of non‐labile metals should be taken into account when evaluating metal mobility or predicting their transport.     

Aquatic mosses for the detection and follow-up of accidental discharges in surface waters

Aquatic mosses have been used to study four accidental discharges of the heavy metals Cd, Zn and Hg or the chlorinated hydrocarbons pentachlorophenol (PCP) and lindane in highly contrasting river types. Hg, PCP and lindane moss concentrations reached 880, 4500 and 350 ng g^?1, respectively. In the case of Cd and Zn, water samples and transferred bioindicators were taken simultaneously throughout an accidental discharge. The very high dissolved metal concentrations reached during this accident (9 mg L^?1 Zn, 90 μg L^?1 Cd) induced accumulation by the mosses of up to 28 mg g^?1 for Zn and 225 μg g^?1 for Cd. The increase in concentrations in the mosses was as rapid and substantial as in the water, the time lag due to accumulation kinetics being almost zero. On the other hand, the memory effect enabled mosses to retain marked evidence of Cd, Zn, Hg, PCP and lindane up to 13 days after the accident when difference from background levels can hardly be detected in the water. The four case studies, which killed fish, but not the mosses, show that the previously established scales of quality based on the analysis of aquatic mosses are well suited to estimating the potential damage to the aquatic ecosystem as a whole.     

Sewage sludges in Hawaii: Chemical composition and reactions with soils and plants

Sewage sludges from six wastewater treatment plants in Hawaii were periodically sampled to determine the seasonal variation of their elemental composition. The Sand Island and Honouliuli treatment plants produced primary sludges averaging 1.6% and 2.0% total N, respectively. The Kailua, Kaneohe, Waimanalo, and Waianae treatment plants produced secondary sludges averaging 5.4, 5.1, 6.1, and 3.5% N, respectively. All the sludges tested were virtually devoid of K with concentration ranging from 0.01 to 0.15%, which was less than half of the 0.30% K considered typical for a US sewage sludge. Mean concentrations of Cd, Cu, Fe, Ni, and Zn in the Hawaii sludges were 5.9, 373, 12343, 218, 36.7, and 817 mg kg^?1, respectively, which were within the norms for sludge heavy metals as reported by the US Environmental Protection Agency. Seasonal variations in elemental concentration were small and only statistically significant for Ca and Zn. Sludges from the three treatment plants with highest annual production (Sand Island, Honouliuli, and Kailua) were then mixed at 5, 50, and 250 g kg^?1 with three representative tropical soils (a Mollisol, and Oxisol, and an Ultisol) to study sludge-soil reactions and plant responses. Soil-solution data indicated that chemical properties of a sludge-soil mixture depended not only on the soil, sludge, and its application rate, but also on sludge-soil interactions. At an agricultural rate of 5 g kg^?1 (10 Mg ha^?1), the anaerobically digested Kailua sludge increased corn (Zea mays L.) biomass, whereas the two undigested sludges reduced it. At higher rates, Mn phytotoxicity resulted from sludge applications to the Mollisol and Oxisol, both of which contained reducible Mn nodules. Significant growth reductions would be expected when corn seedlings contained ≥200 mg Mn kg^?1 or ≤0.30 % Ca; and, adequate supplies of Ca and Zn seemed to lessen Mn phytotoxicity.