赤泥对污染土壤Pb、Zn化学形态和生物可给性的影响

通过土壤培养实验,研究添加赤泥对污染土壤中Pb、Zn化学形态和生物可给性的影响。结果表明,不同赤泥用量处理均可显著降低土壤中HOAc提取态Pb、Zn含量。当赤泥用量为5%时,培养1、2和3个月后,HOAc提取态Pb含量分别比对照下降62.5%、65.3%和73.5%;HOAc提取态Zn含量分别比对照下降56.7%、65.8%和67.4%。培养3个月后,只有1%赤泥用量处理显著降低了土壤中生物可给性Pb含量,而不同用量赤泥处理均显著降低了土壤中生物可给性Zn含量。研究表明赤泥是一种钝化污染土壤中Pb、Zn的潜力添加剂。     

堆肥和腐殖酸对土壤锌铅赋存形态的影响

通过实验室土壤培养实验,研究2种有机物质——腐殖酸和堆肥,单独或者复合应用对土壤中铅锌形态转化的影响。经过1～3个月的培养,发现单独添加腐殖酸和堆肥均可以显著改变土壤中Zn、Pb形态转化,使它们从容易被植物吸收利用的交换态和碳酸盐结合态向难以被植物吸收利用的有机结合态和残渣态转化。与对照相比,单独添加10%堆肥和5%腐殖酸并培养1～3个月后,导致土壤交换态Zn比重分别由38%～51%下降到14%～21%和26%～46%;铁锰氧化物结合态Zn比重分别由23%～34%提高到33%～56%和26%～45%;碳酸盐结合态Pb比重分别由12%～25%下降到1%～15%和2%～15%;残渣态Pb比重分别由12%～14%提高到32%～45%和20%～23%。其他结合态的Zn和 Pb比重也有不同程度的变化。说明堆肥和腐殖酸均可以固定土壤中的Zn和 Pb。而当两者一起使用时,可以中和它们各自所引起土壤pH的变化,而对重金属固定效率更明显增强。研究还发现,不管是腐殖酸还是堆肥,对Pb的固定效果均好于对Zn的固定。     

改良剂对土壤Cu形态转化及其生物可给性的影响

通过室内土壤培养实验,研究添加9种不同改良剂(沸石、石灰、磷矿粉、油菜秸秆、堆肥、赤泥、生物调理剂、生物炭和骨炭)对污染土壤Cu化学形态和生物可给性的影响。培养2个月,除堆肥处理外,添加5%的其他8种改良剂均显著地提高了土壤的p H值,提高效果为石灰生物炭赤泥生物调理剂油菜秸秆=骨炭磷矿粉沸石。培养2个月后,添加所有改良剂均显著地降低了土壤中酸可提取态Cu的含量,生物调理剂、生物炭和骨炭处理效果最为显著,分别比对照下降28%、18.1%和33.7%。添加不同的改良剂对土壤Cu的生物可给性也有影响。培养1个月,石灰、生物炭和骨炭处理分别导致土壤中生物可给性Cu含量比对照降低9.8%、10.5%和18.3%;培养2个月,赤泥、生物炭和堆肥处理分别导致生物可给性Cu含量比对照降低13.2%、17.6%和18.6%。研究表明,生物炭和骨炭可作为Cu污染土壤的理想改良剂。     

矿物材料对Cd污染土壤中Cd的钝化效果

采用土壤培养实验,研究了海泡石、钙基膨润土、钠基膨润土、汉白玉和石灰5种矿物材料在3个添加量下对Cd污染土壤p H和CEC、Cd植物有效性、浸出毒性和生物可给性以及Cd形态分布的影响。结果表明:几种矿物材料均可显著提高土壤p H和CEC。与对照相比,添加几种矿物材料后土壤p H提高0.46~1.15个单位,CEC增加5.8%~39.3%,其提高幅度随添加量的增加而增大。添加矿物材料显著降低土壤Cd的植物有效性(DTPA-Cd)、浸出毒性(TCLP-Cd)和生物可给性(SBET-Cd),且DTPA-Cd、TCLP-Cd和SBET-Cd含量的降低比例分别为9.4%~27.5%、6.4%~23.8%和7.7%~20.5%。添加几种矿物材料后,土壤中酸提取态Cd含量显著降低,残渣态Cd含量显著增加,可还原态和可氧化态Cd含量无明显变化。与对照相比,土壤酸提取态Cd含量降低6.2%~31.4%,残渣态Cd含量增加2.8%~9.7%。几种矿物材料中,海泡石和汉白玉对土壤Cd钝化效果相当,且优于其他矿物材料。     

改性沸石对土壤铅、锌赋存形态的影响简

通过室内土壤培养实验,研究改性沸石对污染土壤中Pb、Zn赋存形态的影响。结果表明,土壤中的Pb主要是以Fe-Mn氧化物结合态存在,土壤Zn主要以残渣态存在。添加天然沸石和改性沸石不同程度地降低土壤酸提取态Pb、Zn的含量,提高土壤残渣态Pb、Zn的含量。与CK处理相比,添加4种沸石导致土壤酸提取态Pb含量降低8.7%~40.3%,土壤酸提取态Zn含量降低10.5%~49.8%（培养1个月）。硝酸钾改性沸石比天然沸石更能显著地降低土壤酸提取态Pb、Zn的含量,而氢氧化钠改性沸石和硝酸钾改性沸石比天然沸石更能显著地降低土壤酸提取态的Zn含量。培养1、2和3月后,不同沸石处理导致土壤残渣态Zn比率分别比CK处理提高14.4%~23.5%、19.6%~23.7%和1.9%~11.1%。研究结果表明,天然沸石经过一定方法改性后,是固定污染土壤Pb、Zn的潜在改良剂。     

施用污泥堆肥对草莓生长及土壤重金属的影响

通过施用污泥堆肥盆栽种植草莓,研究施用不同比例(0%、5%、10%和20%)的城市污泥堆肥对土壤及草莓果实重金属含量的影响以及土壤重金属生物有效态的变化,为污泥堆肥在农业利用方面提供相关理论支撑。实验结果表明:不同污泥堆肥施用比例处理草莓产量大小顺序为:5%0%(CK)10%20%(死亡),污泥堆肥施用比例为5%时,草莓果实的产量(鲜重)达最大值每株5.34 g,高出CK处理32.32%。施肥土壤中的重金属Cu、Zn、Pb、Cr和Cd等含量均随污泥施用比例的增加而呈差异显著水平增加。对比2015年1月27日和3月24日2次采摘的草莓果实重金属含量,第二次采摘的果实Cu、Zn含量比第一次采摘的果实含量有不同程度的增加,而Pb、Cd和Ni含量有不同程度的降低。在污泥堆肥施用比例为5%时,施肥土壤以及草莓果实中的重金属含量均未超过国家相关标准。种植植物后施肥土壤中重金属Cu和Zn的生物有效态增加,重金属Pb、Ni的生物有效态降低。因此,适量施用污泥堆肥能有效增加草莓产量,5%的施用比为草莓种植的最佳施肥比例。     

高温堆肥与蚯蚓堆肥对城市污泥重金属形态的影响

采用高温堆肥和蚯蚓堆肥工艺,研究了城市污泥与锯末、粉煤灰或磷矿粉按不同比例混合堆肥前后重金属（Cu、Pb、Zn、Cd和As）交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残留态的变化。研究表明：高温堆肥和蚯蚓堆肥前后各试验污泥的重金属形态和含量呈现出不同的变化,都可以降低污泥中交换态Cu、Pb、Zn、Cd和As的含量;对于Cu和Pb,高温堆肥优于蚯蚓堆肥;对于Zn、Cd和As,蚯蚓堆肥优于高温堆肥。2种堆肥方式中,粉煤灰用量为10%的钝化效果优于20%,磷矿粉的钝化效果同粉煤灰一样。     

改良剂对重金属复合污染土壤的修复效果

为揭示不同改良剂及其联合施用对重金属复合污染土壤的修复效果,采用室内土壤培养实验和室外盆栽实验相结合,研究不同施用量(10和20 g·kg~(-1))的蛭石(A)、泥炭(B)和骨粉(C)以及两两组合施用下,改良剂对土壤重金属DT-PA有效态、植物(以空心菜为例)生物量、株高以及植物可食部重金属含量的影响。结果表明:不同处理条件下的土壤p H值的提升与空白对照相比变化不显著;单施2%泥炭对土壤重金属Cu、Zn的钝化效果优于其他处理组,相对空白对照组,在第42天2种金属有效态含量分别降低了57.65%和65.55%,而1%蛭石和1%骨粉的混合添加能有效降低土壤中有效态Cd含量,相对空白对照组在第42天有效态Cd含量降低了40.52%;3种改良剂单施和混施对空心菜均具有增产增收的显著效果,且混施改良剂对空心菜增产效果较好;各处理组中空心菜体内Cu、Zn和Cd含量均有显著的降低,其中2%泥炭、1%蛭石+1%泥炭和1%蛭石+1%骨粉处理组分别对空心菜体内Cu、Zn和Cd含量降低效果最好,相对空白对照组分别降低了75.39%、70.75%和75.42%。因此,在该污染类型土壤泥炭、蛭石+泥炭和蛭石+骨粉分别对空心菜吸收土壤中的Cu、Zn和Cd具有较好的阻控效果。     

赤泥添加对石灰性土壤中Pb、Cd形态分布及小麦根系的影响

通过田间种植小麦实验,研究添加不同剂量拜耳赤泥(0%、1%、2%、3%、4%和5%)对重金属污染的石灰性土壤Pb、Cd化学形态和小麦幼苗根系的影响。培养1个月,添加赤泥显著地提高了土壤p H值,提高幅度随赤泥投加量增加而增大。培养3个月,添加不同剂量的赤泥均明显降低土壤中可交换态Pb和Cd的含量,赤泥投加量为5%时效果最为显著,分别比对照下降90%和72%。添加赤泥对所种植小麦幼苗的根系也有影响。种植5个月,小麦根系总根长、总表面积和总体积等随添加赤泥的剂量增加呈现先增大后减小的趋势,赤泥投加量为3%时增幅最大,总根长、总表面积和总体积分别比对照增加88.23%、75%和90.32%。研究表明,赤泥可作为重金属污染的石灰性土壤的理想改良剂,但考虑到小剂量赤泥(即1%~3%)促进重金属污染农田中小麦根系的生长,建议在种植区采用小剂量赤泥(即3%)处理的重金属污染修复方案。     

大田条件下施加组配改良剂对蔬菜吸收重金属的影响

通过向湘南某矿区周边重金属污染的农田施加不同添加量(0、2、4和8 g/kg)的组配改良剂HS(海泡石+石灰石),分析农田土壤理化性质变化和土壤重金属及其交换态含量的影响、空心菜和辣椒可食部位和根部位重金属含量的影响。结果表明,施用2~8 g/kg组配改良剂HS能使2种蔬菜土壤p H值和CEC含量显著增加,使交换态重金属含量大幅降低,且不同程度地降低了空心菜和辣椒可食部位及根部位的重金属含量。与对照相比,空心菜和辣椒可食部位重金属Pb、Cd、Cu、Zn的降幅分别为:21.1%~47.5%、6.5%~31.0%、57.7%~80.0%、65.3%~92.0%和27.3%~74.5%、29.8%~62.0%、55.4%~76%、37.8%~77.1%;根部位的重金属含量也有明显降低。当添加量为8 g/kg时,2种蔬菜可食部位和根部位重金属含量降低幅度最大。由此可知,组配改良剂HS的施用对2种蔬菜吸收土壤重金属起到有效的抑制作用。     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death,age, and season

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 microg/m3 particulate matter (PM) of median diameter < or = 10 microm (PM10); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO2; 1.6% (1.1-2.0%) per 31.2 ppb O3; and 0.9% (0.7-1.2%) per 9.4 ppb SO2 (daily maximum concentration for O3, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM10 and SO2. Larger effect sizes were observed for respiratory mortality for all pollutants except O3. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Meta-Analysis of Time-Series Studies of Air Pollution and Mortality: Effects of Gases and Particles and the Influence of Cause of Death,Age, and Season

Abstract

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 μg/m³ particulate matter (PM) of median diameter <10 μm (PM₁₀); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO₂; 1.6% (1.1-2.0%) per 31.2 ppb O₃; and 0.9% (0.7-1.2%) per 9.4 ppb SO₂ (daily maximum concentration for O₃, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM₁₀ and SO₂. Larger effect sizes were observed for respiratory mortality for all pollutants except O₃. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

骆马湖富营养化和生态状况调查与评价

为了了解骆马湖水质状况，在2005年对骆马湖富营养化状态和生态特性进行了调查，并结合“十五”期间的监测资料进行了分析。2005年骆马湖水体中总氮和总磷的平均值超《地表水环境质量标准》（GB3838-2002）中Ⅲ类，超标情况分别为0．78倍和0．54倍，达到湖库特定项目Ⅳ类水标准，骆马湖处于轻度富营养化状态。对骆马湖生态特征分析表明，由于该湖泊的形态以及“藻型浊水状态”和“泥沙型浊水状态”交替出现，遏制了湖水从高营养盐含量向全面富营养化状态演变，保障了底栖动物的良好生长环境，从而形成了骆马湖独特的环境生态平衡。     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

Adsorption of molybdate and tetrathiomolybdate onto pyrite and goethite: effect of pH and competitive anions

The adsorption of two major molybdenum (Mo) species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)) onto two main iron minerals pyrite (FeS2) and goethite (FeOOH) is addressed to elucidate the possible mechanisms of molybdenum immobilization in anoxic sediments. Suspensions of MoS4(2-) (or MoO4(2-)) and goethite (or pyrite) in 0.1M NaCl solution were equilibrated under anoxic conditions at 25 degrees C in the pH range from 3 to 10. The competitive effects of sulfate, phosphate, and silicate on the adsorption of MoO4(2-) and MoS4(2-) by pyrite and goethite are also addressed. Adsorption of MoO4(2-) and MoS4(2-) on pyrite and goethite is in general well described by a Langmuir model at low pH; the extent of sorption is a function of pH and the surface loading. Maximum sorption is observed in the acidic pH range (pH<5) at low surface loading. The adsorption of molybdenum (micromol g(-1)) depends upon Mo species and on the type of iron mineral following the order: MoS4(2-)-goethite > MoO4(2-)-goethite > MoS4(2-)-pyrite > MoO4(2-)-pyrite. Phosphate appears to compete strongly with MoO4(2-) and MoS4(2-) for the sorption sites of pyrite and goethite. The strength of the phosphate competitive effect follows the sequence of MoO4(2-)-goethite approximately = MoO4(2-)-pyrite > MoS4(2-)-pyrite > MoS4(2-)-goethite. Silicate and sulfate have a negligible effect on the sorption of MoO4(2-) and MoS4(2-). The preferred adsorption by iron mineral of MoS4(2-), as well as its behavior in the presence of competitive anions suggests that tetrathiomolybdate species may be an ultimate reservoir and may control Mo enrichment in the sediments.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.