Freshwater Ulva (Chlorophyta) as a bioaccumulator of selected heavy metals (Cd, Ni and Pb) and alkaline earth metals (Ca and Mg)

We analyzed the ability of freshwater taxa of the genus Ulva (Ulvaceae, Chlorophyta) to serve as bioindicators of metal in lakes and rivers. Changes in heavy metal (Ni, Cd and Pb) and alkaline earth metal (Ca and Mg) concentrations in freshwater Ulva thalli were investigated during the period from June to August 2010. The study was conducted in two ecosystems in Western Poland, the Malta lake (10 sites) and the Nielba river (six sites). Three components were collected for each sample, including water, sediment and Ulva thalli. The average concentrations of metals in the water sample and in the macroalgae decreased in the following order: Ca > Mg > Ni > Pb > Cd. The sediment revealed a slightly altered order: Ca > Mg > Pb > Ni > Cd. Ca and Mg were found at the highest concentrations in thalli due to the presence of carbonate on its surface. Among the examined heavy metals in thalli, Ni was in the highest concentration, and Cd found in the lowest concentration. There were statistically significant correlations between the levels of metals in macroalgae, water and sediment. Freshwater populations of Ulva exhibited a greater efficiency to bioaccumulate nickel as compared to species derived from marine ecosystems.     

Formation of chlorinated hydrocarbons during combustion of poly (vinyl chloride)

Pilot-scale experiments were carried out to study the formation of chlorinated hydrocarbons through combustion of PVC. Vinyl chloride, dichloro-, trichloro-, tetrachloro-, pentachloro-, and hexachlorobenzenes were determined by GC/ECD. Furthermore, some peaks in the chromatogram were tentatively assigned to octachlorostyrene and PCB. The total amount of lipophilic organochlorinated compounds was determined by neutron activation analysis. The results indicate that incineration of PVC is not a major source of chlorinated hydrocarbons in the environment.     

Emission reduction of aluminium anodising industry by production of Mg2+-Al3+-SO4(2-) -hydrotalcite-type compound

The synthesis of Mg(2+)-Al(3+)-SO(4)(2-)-hydrotalcite-type compound from the acid wastewaters of the aluminium anodising industry has been studied as a possible way of reducing the emissions to the environment, recovering simultaneously resource materials as a valuable mineral. The process of synthesis was carried out using rinse wastewater solutions generated from the anodising treatment when a cascade rinsing system is employed. The method of co-precipitation at constant pH was employed for such a process, using MgO as a source of magnesium. The synthesis was studied as a function of precipitation pH (8-10) and flow rate of reagent mixture (5-30 ml min(-1)). High pH of precipitation and low flow rate of reagent mixture (5-15 ml min(-1)) were found optimal to improve the crystallinity of the synthesised product. The mineral characterisation was performed using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis and differential thermal analysis, all of which indicated characteristics typical of the desired compound. Almost 100% of the aluminium initially present in the acid wastewater solutions was recovered in the form of Mg(2+)-Al(3+)-SO(4)(2-)-hydrotalcite-type compound.     

Formation and chlorination of polychlorinated naphthalenes (PCNs) in the post-combustion zone during MSW combustion

Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simultaneously at three different temperatures (450 degrees C, 300 degrees C and 200 degrees C, respectively) in the post-combustion zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homologue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with successive reductions in abundance with each additional degree of chlorination. The isomer distribution patterns reflected ortho-directionality behavior of the first chlorine substituent, and the beta-positions, i.e. the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the post-combustion zone resulted in increased PCN levels at 200 degrees C, demonstrating the occurrence of chlorination reactions in the post-combustion zone. However, the increases were restricted to the least-chlorinated homologue (monoCN), probably because there was insufficient residence time for further chlorination. In addition, an episode of poor combustion (manifested by high CO levels) was accompanied by extensive formation of 1,8-diCN, 1,2,3- and 1,2,8-triCN; congeners with substitution patterns that are not thermodynamically favorable. These are believed to be products of PAH breakdown reactions and/or chlorophenol condensation. Overall, PCN formation is likely to occur via more than one pathway, including chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlorophenol condensation.     

Determination of sulfur oxides formed during the S(IV) oxidation in the presence of iron

The reaction products (i.e., sulfate (SO4(2-)) and dithionate (S2O6(2-))) of S(IV) oxidation in the presence of iron(III) under different experimental conditions were investigated. Ion-interaction chromatography was used for the separation of sulfate and dithionate using tetrabutylammonium hydroxide (TBAOH) as an ion-pair reagent. The chromatographic method was optimized by varying the composition of the mobile phase (i.e., concentration of TBAOH, acetonitrile and Na2CO3) and by varying the flow rate of the mobile phase. The method was successfully applied to the determination of dithionate formed during the S(IV) oxidation in the presence of Fe(III). In air-saturated solutions sulfate was observed as the only product, while in N2-saturated solutions dithionate was also determined, but it is the minor reaction product and represents about 4% of the total amount of oxidized HSO3- under the studied conditions.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

改性Fe2O3脱硫剂脱除H2S反应特性

为了提高zk-4型Fe2O3脱硫剂脱除沼气中H2S气体的速率,缩短反应的时间,首先搭建了利用容量法测量气固化学反应速率的测试装置,并使用1 mol/L的KF、 NaOH 、KOH碱性溶液对原始脱硫剂进行浸泡、烘干处理,然后对所得3种处理过的脱硫剂与原脱硫剂进行吸附脱硫实验研究,最终得出实验过程中H2S气体摩尔浓度的变化趋势、4种脱硫剂最大反应速率与H2S摩尔浓度的关系式、反应初期阶段相应的反应级数和4种脱硫剂的最大反应速率的排列次序,在反应初始阶段的最大脱硫速率关系依次为r(AKOH)> r(ANaOH)> r(AKF)> r(A0)。     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.     

磷酸铵镁Mg(OH)_2碱促热解动力学

考察了Mg(OH)_2辅助碱性介质对磷酸铵镁降解的媒介作用,解析了磷酸铵镁热解动力学过程。Mg(OH)_2碱促热解为3步降解过程,5 K/min时,其最大吸热峰为390 K;Mg(OH)_2碱促热解动力学降解模型符合自催化降速模型,存在2种以上的降解途径;氨基剥离所需活化能在34.4~112.9 k J/mol之间,Mg(OH)_2碱促热解动力学方程为:f(α)=k_0(1-α)~n,线性相关系数为0.994,反应级数为6.12。     

Effects of high dose copper on plant growth and mineral nutrient (Zn,Fe, Mg,K, Ca) uptake in spinach

Loessal soil is one of the main cultivated soils in northwest China. Part of its distribution area was irrigated with industrial wastewater in past three decades. This caused heavy metal contamination in the soil. It had induced toxicity on crops and also threatened local human health for now. Based on a field plot experiment, effects of different Cu concentrations (from 45 to 2000 mg kg^?1) in loessal soil on spinach plant growth and uptake of mineral nutrients (Zn, Fe, Mg, K, and Ca) by spinach were investigated. The Cu addition increased available concentrations of mineral nutrients in loessal soil and concentrations of Cu, Zn, Mg, and Ca in roots. The translocation of mineral nutrients from roots to leaves was inhibited under Cu addition, inducing their decrease in leaves. The EC₁₀ and EC₅₀ of soil Cu in relative dry weights of leaves were 240.33 mg kg^?1 and 1205.04 mg kg^?1, respectively. The PLS-PM analysis showed that available concentrations of nutrients in soil were only affected by Cu in soil positively, nutrients in roots were mainly affected by Cu in soil and Cu in leaves positively, nutrients in leaves were mainly affected by Cu in roots negatively, translocation of nutrients in spinach and plant growth were principally affected by Cu in leaves negatively, and the total effect of Cu in leaves on nutrients in roots and leaves, translocation of nutrients in spinach, and plant growth was the highest. Our results indicated that the phytotoxicity of Cu including spinach growth inhibition and mineral disorder in spinach was mainly affected by the Cu concentrations in leaves.

     

The formation of dithionate during the iron(III)-catalysed autoxidation of sulfur(IV)-oxides

The iron(III)-catalyzed autoxidation of sulfur(IV)-oxides results in the formation of two different oxidation products of sulfur(IV): dithionate, S₂O₆²⁻, and sulfate, SO₄²⁻. The yield of these reaction products depends on the experimental conditions. Under the studied conditions ([Fe(III)] : [SIV)] = 1:10, pH = 2–4) dithionate is the minor reaction product. The formation of dithionate is influenced by the initial pH but not by the initial O₂ concentration. The presence of CO²⁺, Mn²⁺, and Ni²⁺ have no influence on the yield of dithionate, whereas in the presence of Cr³⁺ less and, in the presence of Cu²⁺, no dithionate is formed.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

Formation of particulate sulfur species (sulfate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach

To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO₄²⁻) and methanesulfonate (MS_x used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS⁻) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS⁻. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS⁻ levels. The modelling results indicate that about 80% of the production of MS⁻ can be attributed to heterogeneous reactions.Observed submicron nss-SO₄²⁻ levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO₂) to sulfuric acid (H₂SO₄), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO₄²⁻ can be explained by condensation of gas-phase H₂SO₄, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO₂ and H₂SO₄) in good agreement with earlier estimates for the area.     

Pseudomonas S2-3菌株对Cr(VI)的耐受性及去除

针对分离得到的Cr(VI)耐受菌株S2-3进行了基本生长特征、16S rRNA序列分析、Cr(VI)对菌株生长影响、菌株生长代谢与铬的去除的关系等研究。结果表明:该菌株属于假单胞菌,与Pseudomonas chlororaphis(Z76673)相似性最高(99.8%);Cr(VI)对菌株生长有着明显的抑制作用,其耐受上限可达到1500 mg/L左右;Cr(VI)导致菌体细胞大小分布变宽,同时使得细胞表面的-OH和-NH基团减少。当初始Cr(VI)浓度为100 mg/L时,48 h内菌株S2-3对Cr(VI)去除效率可达到85.9%,对总铬去除率为24.1%。在高Cr(VI)浓度(1000 mg/L)下,菌株对Cr(VI)和总铬仍有一定的去除效果,分别为58.7%和3.3%。菌株S2-3主要通过还原Cr(VI)的方式去除Cr(VI)。Cr(VI)的还原与菌液ORP以及细胞表面的-OH和-NH有关;总铬的去除不是因为形成了氢氧化铬沉淀,而是Cr(III)被吸附在了细胞表面的-C=O上。     

以Ca（OH）2为pH调节剂的磷酸氢镁吸附法处理氨氮废水的研究

提出了以Ca（OH）2为pH调节剂、磷酸氢镁（MHP）为吸附剂的氨氮废水处理新方法（MHP吸附法）。MHP吸附法的特点是吸附产物磷酸铵镁（MAP）可通过简单的热分解再生MHP,同时回收高浓度氨水。考察了MAP热分解制备MHP的工艺条件;对氯化铵、硫酸铵及碳酸铵3种模拟氨氮废水体系,分别考察了pH值、温度、氨氮初始浓度对MHP吸附容量的影响;考察了MHP的循环使用性能。研究结果表明,MHP对氨氮具有良好的吸附性能,NH4^＋最高达到了约90mg/g。MHP在循环使用中,对低浓度氨氮废水其吸附容量呈下降趋势,但对高浓度氨氮废水具有良好的循环使用性能。