Copper and cadmium complexation by high molecular weight materials of dominant microalgae and of water from a eutrophic reservoir

High molecular weight materials (HMWM, >12000-14000 Da) excreted by the two cyanophyte species (Microcystis aeruginosa and Anabaena spiroides) and a diatom (Aulacoseira granulata) which are dominant phytoplankton species in a eutrophic reservoir, Barra Bonita, Brazil were investigated as copper (Cu) and cadmium (Cd) complexation agents and their monosaccharide and elemental analysis of C, H, N and S determined. Also, HMWM obtained from the reservoir water as well as from a mixture of the three algae materials were studied. The HMWM of the cyanophytes and the mixture of the three algae materials complexed Cu and Cd, whereas the HMWM of the diatom and that from the reservoir water complexed only Cu. Two classes of ligands of intermediate to weak binding strength were obtained after Scatchard plot analysis of the titration data. The cyanophytes and the mixture HMWM presented higher conditional stability constants for Cu class-1 ligands (logK1' = 9.2-9.5) than the HMWM derived from the diatom and the reservoir water (logK1' = 8.6-8.8). Higher proportions of acidic monosaccharides corresponded to higher K1' of Cu and Cd complexation, yet no relation was observed among complexation parameters and elemental analysis. This study points out Cu ligands of intermediate to weak binding strength in the excreted HMWM of dominant microalgae and in the HMWM of the reservoir water, while Cd was solely complexed by ligands isolated from the cyanophyte HMWM.     

The effect of pH, ion strength and reactant content on the complexation of Cu2+ by various natural organic ligands from water and soil in Hong Kong

The complexation constants for copper associated with different natural organic ligands, including dissolved organic carbon (DOC) extracted from water, water soluble organic carbon (WSOC), fulvic acid (FA) and humic acid (HA) from soil, were determined and then compared based on discrete single site model. Both ion-selective electrode (ISE) and anodic stripping voltammetry were used to determine the content of free copper ions, while the relative number of complexation sites was estimated using a fluorescence quenching (FQ) at the same time. ISE proved to be the most applicable technique when the concentration of copper was above 10(-7) moll(-1). The logk values for two WSOC sample sites (Song Ziyuan and Xin Niangtan) were 4.64 and 4.66; higher than both the DOC and HA values yet lower than the FA values, which were unusually high due to unavoidable pollution from the cation exchange resin used during the purification process. Binding affinities between the copper ions and the organic ligands obtained from streams in Yong Wei (DOC) and Song Ziyuan (WSOC) were influenced by pH, ion strength, and reactant concentration. Values for logk increased with increases in pH (ion strength of 0.1 N). At pH 4, the logk values decreased with increases in the supporting electrolyte concentration and total copper ion additions.     

Fine and coarse particulate matter chemical characterization in a heavily industrialized city in central Mexico during Winter 2003

This paper presents the results of the first reported study on fine particulate matter (PM) chemical composition at Salamanca, a highly industrialized urban area of Central Mexico. Samples were collected at six sites within the urban area during February and March 2003. Several trace elements, organic carbon (OC), elemental carbon (EC), and six ions were analyzed to characterize aerosols. Average concentrations of PM with aerodynamic diameter of less than 10 microm (PM10) and fine PM with aerodynamic diameter of less than 2.5 microm (PM2.5) ranged from 32.2 to 76.6 [g m(-3) and 11.1 to 23.7 microg m(-3), respectively. OC (34%), SO4= (25.1%), EC (12.9%), and geological material (12.5%) were the major components of PM2.5. For PM10 geological material (57.9%), OC (17.3%), and SO4= (9.7%) were the major components. Coarse fraction (PM,, -PM2.5), geological material (81.7%), and OC (8.6%) were the dominant species, which amounted to 90.4%. Correlation analysis showed that sulfate in PM2.5 was present as ammonium sulfate. Sulfate showed a significant spatial variation with higher concentrations to the north resulting from predominantly southwesterly winds above the surface layer and by major SO2 sources that include a power plant and refinery. At the urban site of Cruz Roja it was observed that PM2.5 mass concentrations were similar to the submicron fraction concentrations. Furthermore, the correlation between EC in PM2.5 and EC measured from an aethalometer was r(2) = 0.710. Temporal variations of SO2 and nitrogen oxide were observed during a day when the maximum concentration of PM2.5 was measured, which was associated with emissions from the nearby refinery and power plant. From cascade impactor measurements, the three measured modes of airborne particles corresponded with diameters of 0.32, 1.8, and 5.6 microm.     

Effects of copper concentration on methane emission from rice soils

Outdoor pot experiments with various paddy soils representing five soil types were conducted at Nanjing Agricultural University during the 2000 and 2001 rice-growing seasons. Eighteen soils and ten out of the eighteen soils were involved in the 2000 and the 2001 experiment, respectively. Two treatments were designed as mineral fertilization (MF) and mineral fertilizer + wheat straw incorporation (MF + WS) for the 2001 experiment. Seasonal average rate of CH4 emission from different soils ranged from 1.96 to 11.06 mg m(-2) h(-1) in the 2000 experiment, and from 0.89 to 5.92 mg m(-2) h(-1) for the MF treatment in the 2001 experiment, respectively. Incorporation of wheat straw enhanced considerably CH4 emission with an average increment of 7.09 mg m(-2) h(-1). CH4 emissions from the two-year experiment were negatively correlated to soil available and total copper concentration. A further investigation showed that CH4 emission from the MF treatment was positively related to the dissolved organic carbon (DOC) in the soil (r = 0.904, p < 0.001), and that the DOC was negatively correlated to the concentrations of available copper (r = -0.844, p < 0.01) and total copper (r = -0.833, p < 0.01), respectively. Nevertheless, the incorporation of wheat straw did not enhance the soil DOC, and the relationship between CH4 emission and soil DOC was not statistically significant (r = 0.470, p < 0.20). It was concluded that higher concentration of copper in the soils resulted in lower soil DOC and thus reduced CH4 emission when there was no additional organic matter input. Incorporation of wheat straw did not affect soil DOC and available copper concentration but enhanced CH4 emission.     

Evidence of recycling of lead battery waste into highly leaded jewelry

Inexpensive highly leaded jewelry, much of it imported from China, remains widely available in the United States. The source materials for these items are unknown. Due to the low cost of much of this trinket jewelry, it seems likely that scrap materials may be used in their manufacture. Thirty-nine jewelry items previously determined to contain 90% or more lead by weight were analyzed for antimony content. The average antimony content of these thirty-nine items was 3.0%. The range of antimony content in the samples was from 0.3% to 6.2% antimony by weight, with twenty-seven of the samples in the range of 2-4% antimony by weight. By comparison, battery lead standard reference material obtained from the US National Institute of Standards and Technology contains 2.95% antimony by weight. While the evidence is circumstantial, the similarity in composition of these samples to battery lead is striking and supports the hypothesis that some battery lead is being recycled into highly leaded jewelry items. These results suggest that the recycling of this waste in China needs to be investigated, as the use of lead battery waste as a source material for children's jewelry poses a clear threat to children's health.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Leaded electronic waste is a possible source material for lead-contaminated jewelry

Highly leaded jewelry, often imported from China, remains widely available in the United States. Leaded electronic waste is exported from the United States to several Asian countries where solder is recovered and circuit boards are stripped of parts in small workshops. To assess whether electronic waste is being recycled into the jewelry, lead, tin and copper content of highly leaded jewelry samples were determined by atomic absorption spectrometry. Sixteen jewelry items previously determined to contain 20-80% lead by weight were analyzed. Samples were digested in nitric acid for analysis of lead and copper, and in aqua regia for analysis of tin. Six samples contained significant amounts of tin, from 20.8% to 29.9% by weight. In addition, copper was a significant minor component of five of these samples (up to 4% by weight). Copper (present at 10-40% by weight in circuit boards) was shown to rapidly move into heated lead-tin solder. The combined lead-tin-copper content of these six items ranges from 93.5% to 100%, suggestive of a solder-based source material. These results are consistent with the hypothesis that recycled circuit board solders are being used to produce some of the heavily leaded imported jewelry sold in the United States. Should this hypothesis be substantiated, it suggests that environmental policies to protect children's health must address both proper recycling of source materials as well as restrictions of the lead content in consumer goods.     

Copper and trace element fractionation in electrokinetically treated methanogenic anaerobic granular sludge

The effect of electrokinetic treatment (0.15 mA cm(-2)) on the metal fractionation in anaerobic granular sludge artificially contaminated with copper (initial copper concentration 1000 mg kg(-1) wet sludge) was studied. Acidification of the sludge (final pH 4.2 in the sludge bed) with the intention to desorb the copper species bound to the organic/sulfides and residual fractions did not result in an increased mobility, despite the fact that a higher quantity of copper was measured in the more mobile (i.e. exchangeable/carbonate) fractions at final pH 4.2 compared to circum-neutral pH conditions. Also addition of the chelating agent EDTA (Cu2+:EDTA4- ratio 1.2:1) did not enhance the mobility of copper from the organic/sulfides and residual fractions, despite the fact that it induced a reduction of the total copper content of the sludge. The presence of sulfide precipitates likely influences the copper mobilisation from these less mobile fractions, and thus makes EDTA addition ineffective to solubilise copper from the granules.     

Evaluation of cadmium, copper, zinc, and iron concentrations and tissue distributions in the benthic crab, Dorippe granulata (De Haan, 1841) from Tolo Harbour, Hong Kong

The distributions of copper, zinc, iron, and cadmium among the tissues of Dorippe granulata were determined. The highest copper concentrations were found in the haemolymph (c. 53 microg ml(-1)) while the highest iron concentrations occurred in the gills (c. 720 microg g(-1) dry weight) and the highest zinc concentrations in the exoskeleton (c. 200 microg g(-1) dry weight). By comparison, concentrations of the non-essential metal, cadmium, were low in all tissues (mean = 10 microg g(-1) dry weight). The highest value was recorded from the midgut gland of a female crab (18.5 microg Cd g(-1) dry weight). Concentrations of copper, zinc, and iron were positively correlated with tissue-hydration levels. Such a relationship was not found for cadmium. The findings are discussed with regard to trace-metal levels found in temperate and tropical brachyurans from clean and polluted localities.     

Modified SBA-15 mesoporous silica for heavy metal ions remediation

N-Propylsalicylaldimino-functionalized SBA-15 mesoporous silica was prepared, characterized and used as an adsorbent for heavy metal ions. The organic-inorganic hybrid material was obtained using successive grafting procedures of SBA-15 silica with 3-aminopropyl-triethoxysilane and salicylaldehyde, respectively. For comparison an amorphous silica gel was functionalized using the same procedure. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis and FTIR spectroscopy. The organic functional groups were successfully grafted on the SBA-15 surfaces and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids for the adsorption of heavy metals ions from aqueous solutions was investigated. The hybrid materials showed high adsorption capacity and high selectivity for copper ions. Other ions, such as nickel, zinc, and cobalt were adsorbed by the modified SBA-15 material. The adsorbent can be regenerated by acid treatment without altering its properties.     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Riverine inputs of organic carbon and nitrogen to Norwegian coastal areas

The transport of organic and inorganic material in 10 Norwegian rivers has been monitored from 1990 to 1998. The suspended material in the rivers consisted of 40-80% organic materials. A major part of this was DOC with a C/ N mole ratio > 25. The C/N ratio of the organic material increases with increasing river flow when drained from forest-dominated catchments, in contrast to mountain dominated catchments where variation in runoff does not influence the C/N ratio. Laboratory experiments showed that more than 90% of the DOC remained in solution when salinity increased to 30. The flocculated and settled material contained less than 5% organic material with a C/N ratio of 6.7-12.4, comparable to C/N ratios in cultivated soils and coastal marine sediments. This confirms that only a minor amount of organic material carried to the sea by rivers settles in the coastal zone.     

The role of copper(II) chloride in the formation of organic chlorine in fly ash

In the de-novo synthesis and formation of PCDD/PCDF, the transfer of inorganic chlorine to the carbonaceous material of fly ash plays an important role. Here, copper acts as a catalyst in the chlorination reaction. In experiments in the range of 250-350 degrees C under helium, we determined the stoichiometry of the chlorination reaction with model systems. Therefore, it was necessary to develop a method to quantify the copper(II) and copper(I) ions. In a combination of solid electron paramagnetic (spin) resonance spectroscopy (EPR) for Cu(I), and X-ray fluorescence spectroscopy (XRFA) analysis for Cu (total), we found a way for the quantification of copper(I) and (II). With these experiments, we can show that the chlorination reaction is relatively fast and comes to a stop under helium, after the copper(II) is reduced. The ratio between the organic chlorine formed and copper(II) reduced is, at the end of the reaction, 0.5, which is in agreement with the following reaction: 2CuCl2 + R-H-->2CuCl + R-Cl + HCl.     

Copper complexation in coastal rainwater,southeastern USA

Complexation of dissolved copper (Cu) was studied in Atlantic coastal rainwater using adsorptive cathodic stripping voltammetry (ASCV) with salicylaldoxime as a competing ligand at pH 7.8. Detectable concentrations of strong Cu-complexing ligands possessing conditional stability constants of 10¹³–10¹⁶ were observed in over 80% of the rain events occurring over the course of 2 year. In 11 of the 23 samples analysed, total dissolved Cu concentrations were higher than those of dissolved ligands, indicating that a significant fraction of the Cu occurred as the free ion and as weaker complexes. In the remaining samples, ligand concentrations were equal to or greater than Cu concentrations, indicating virtually complete (>99%) complexation of the ambient Cu. By varying the analytical detection window, two classes of ligands with differing conditional stability constants were detected in selected rain samples suggesting that the Cu ligands most likely represent a spectrum of organic compounds. Back trajectory analysis indicated that continentally dominated rain samples contained higher concentrations of Cu and organic ligands relative to storms of marine origin, suggesting a strong terrestrial and/or anthropogenic source of both Cu and ligands in rain at this location. Variability in Cu speciation may impact a variety of atmospheric redox reactions because free and complexed forms of the metal have very different reactivities.     

Determination of the aerobic biodegradability of polymeric material in a laboratory controlled composting test

A laboratory method is presented for investigating the biodegradation of an organic test material in an aerobic composting system based on the evolution of carbon dioxide. In addition to carbon conversion, biodegradation can also be monitored through weight loss and physical disintegration. The test method is different from other biodegradation tests, especially aquatic tests, because of the elevated temperature representative for real composting conditions and also because of enhanced fungal degradation activities. A ring test was run using paper and poly-β-hydroxybutyrate/valerate as test materials and cellulose powder as a reference material. The test results and the experience gained by the participants showed that the method is suitable and practicable. Experience with real technical-scale composting facilities confirms that the method provides test results of high predictive value. The test is designed to become a European Standard in connection with determining the compostability of packagings and packaging materials.     

电镀污泥的热处理特性以及对金属回收的影响

焙烧-酸浸法可有效回收电镀污泥中的有价金属,而污泥的热处理特性是决定能否采用焙烧预处理的重要因素。研究了氧化焙烧和还原焙烧对污泥成分和金属浸出性的影响,并对焙烧前后的污泥进行了金属形态分析和X射线衍射(XRD)分析。结果表明,焙烧预处理实现了污泥减量和金属富集;ES1经氧化焙烧后金属浸出率接近原泥,Cu的浸出率达99%;ES2的还原焙烧效果优于氧化焙烧,特别是Cu的浸出率超过97%,XRD分析发现,还原焙烧过程中金属Cu被还原为铁铜合金;2种焙烧均造成了ES3中目标金属Ni的浸出率的降低;金属浸出性的下降与残渣态的形成有关。     

Clear effects of soil organic matter chemistry, as determined by NMR spectroscopy, on the sorption of diuron

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.     

新型净水材料的吸附特性研究

采用高效液相色谱分析微污染水原水、新型材料吸附后出水及活性炭吸附后出水的特征,对比新型材料及活性炭对微污染水中不同分子量的有机物的吸附效果,以此间接反映两种材料的孔径分布特点,分析两种材料的不同吸附特性,并讨论新型净水材料的吸附机理。     

3种水培植物根系分泌的有机酸对氮循环菌的影响

通过收集水培吊兰、空心菜和水芹的根系分泌物,采用液相色谱分析了其中有机酸的种类和含量;并研究了根系分泌物中的有机酸对氮循环菌的影响。结果表明3,种植物根系分泌物中的有机酸对氨化细菌和反硝化细菌的生长具有促进作用,对亚硝化细菌和硝化细菌的生长具有抑制作用。     

Possibilities for improving nitrogen use from organic materials in agricultural cropping systems

Nitrogen release from organic nutrient sources in soil is influenced by a range of factors such as soil temperature and moisture, and chemical composition of the organic material. Chemical composition can, to a certain degree, be controlled to increase the synchronization of nitrogen (N) release with plant N demand, whereas climatic factors cannot be controlled and so must be taken into account when planning management measures. In this paper, we discuss different ways to affect N release through manipulation of the chemical composition of fresh or pretreated plant materials and animal manures, timing of incorporation, and intentional distribution during application. We conclude by giving an overview of off-farm options that may need to be implemented to achieve improved use of N, especially in agricultural systems with surplus N.