赤泥晶种法诱导磷酸铵镁结晶回收模拟废水中磷的可行性研究

对赤泥的理化性质进行了分析,探索了以赤泥为晶种磷酸铵镁(MAP)结晶法从模拟废水中回收磷工艺。结果表明,经过研磨的赤泥颗粒属无孔物质或者大孔物质;将赤泥溶于水时有碱液和离子溶出,赤泥的主要化学成分为Ca、Al、Si和Mg等元素。投加赤泥晶种有利于磷酸铵镁结晶的形成。在初始磷酸盐浓度为90 mg/L、N∶Mg∶P摩尔比为1∶1∶1、不调节pH值、搅拌时间30 min、搅拌速度180 r/min、沉淀时间30 min条件下,赤泥粒径为60～80目、投加量为8 g/L时,以赤泥作为晶种诱导磷酸铵镁结晶回收磷的效果最优。干燥晶种的使用次数对磷酸根离子的回收率影响不大。所得结晶产物是一种很好的缓释肥。     

赤泥活化处理及其除氟剂性能研究

以赤泥为主要原料,采用FeCl3、柠檬酸、聚硅酸等对赤泥进行活化处理,并制成粒径约3mm的球形赤泥除氟剂。采用X射线衍射(XRD)对赤泥除氟剂进行了物相分析,并研究了活化剂种类、活化剂浓度、焙烧温度等对赤泥除氟剂除氟性能的影响。结果表明:3种活化剂中,柠檬酸活化效果最好,而最佳焙烧温度与活化剂的种类有关。采用质量分数为5%的柠檬酸进行活化,焙烧温度500℃、焙烧时间2h的赤泥除氟剂除氟效果最佳,吸附率达99%以上,吸附容量为0.95mg/g,氟离子质量浓度可从19.00mg/L降低到0.07mg/L。     

联合法赤泥的特性及其对水溶液中Pb(Ⅱ)的去除

赤泥作为氧化铝冶炼过程中排出的一般工业固废,具有数量大、碱性强、粒径小、孔隙结构丰富等特征。采用XRF、XRD、SEM/EDX等分析手段,研究了赤泥的化学组成、矿物结构、粒度、比表面积、表面形貌、酸中和能力等特性。通过批实验观测了赤泥对水溶液中Pb(Ⅱ)的去除效果,并对Pb(Ⅱ)初始浓度、pH等影响因子对去除效果的影响展开了分析。结果表明,赤泥的主要化学成分为CaO、SiO_2、Al_2O_3和Fe_2O_3,平均比表面积为43.8 m~2·g~(-1);赤泥有很强的酸中和能力,对硝酸的中和能力约为1.875 mol·kg~(-1)。初始pH=4,且过程中不控制pH时,反应在10 min之内达到平衡,去除率为98%～100%,赤泥对Pb(Ⅱ)的去除能力可达到25.9 mg·g~(-1)。当pH=4时,赤泥对水溶液中Pb(Ⅱ)的去除反应在90～120 min时达到平衡,去除率为10%～45%,当初始浓度为1～100 mg·L~(-1)时,Pb(Ⅱ)初始浓度越高,Pb(Ⅱ)去除能力越强,去除率越低。当pH为7和10时,Pb(Ⅱ)去除率分别为92%和98%,残留Pb(Ⅱ)浓度小于污水综合排放标准中第一类污染物最高允许排放浓度1.0 mg·L~(-1)。通过分析可知,赤泥对Pb(Ⅱ)的去除符合拟二级动力学模型,吸附机理主要为化学吸附。     

不同含水率条件下拜耳法赤泥强度及水力学特性

在利用XRD、XRF、SEM等微观测试手段分析了拜耳法赤泥的化学成分、矿物组成和微观结构的基础上,通过无侧限抗压强度实验、固结排水三轴剪切实验研究了拜耳法赤泥在不同水力路径条件下其强度特性的变化规律;同时通过非饱和土瞬态水力特性循环实验系统对拜耳法赤泥的水力学特性进行了研究。研究表明:含水率的变化对拜耳法赤泥的强度特性有较大程度的影响,在脱水干燥过程中,其抗压强度和抗剪强度指标均有较大程度的增长;拜耳法赤泥具有遇水崩解现象,已干燥硬化的赤泥会遇水崩解,强度指标明显降低,且在较低应变处即发生脆性破坏;拜耳法赤泥的土-水特征曲线和渗透系数特征曲线均展现出明显的滞后效应,说明拜耳法赤泥对水有较大的敏感性,在降雨条件影响下,拜耳法赤泥堆体的稳定性有一定程度的降低。     

不同工况条件混合赤泥力学特性变化规律

在利用常规土工实验和XRF、XRD、SEM等微观测试手段分析了刚出厂混合赤泥化学成分、矿物组成、微观结构的基础上,通过无侧限抗压强度实验和固结排水三轴剪切实验对自然风干、浸水饱和、非饱和-饱和干湿循环3种工况条件下混合赤泥不同龄期力学特性的变化规律进行了研究。结果表明,自然风干试样的无侧限抗压强度和粘聚力要明显大于相同龄期浸水饱和试样和干湿循环试样,说明混合赤泥的强度形成与滤水过程有一定联系,且其强度的增长均主要集中在脱水龄期前70天内;混合赤泥在3种不同工况条件下无侧限抗压强度和粘聚力均有一定程度的增长,说明混合赤泥可在浸水环境下生成不可逆增长的具有水硬性的胶结矿物,使其在水环境中不发生崩解,可保证混合赤泥堆体在自然堆存过程中其力学特性满足安全堆载要求。     

赤泥脱碱及功能新材料研究进展

氧化铝生产过程中产生的赤泥已成为制约铝行业可持续发展的瓶颈。随着铝工业的发展,赤泥的堆存量越来越大,赤泥的综合利用显得尤为迫切。为了解决国内外赤泥的堆存现状及产生的危害,国内外对赤泥资源化利用作了研究,赤泥可以用于生产建筑材料、陶瓷制品、微晶玻璃、路基及防渗材料、硅钙肥、吸附材料和提取有价金属。重点介绍了近年来赤泥脱碱实验研究、赤泥填充塑料、赤泥多元絮凝剂联产复合白炭黑、赤泥免烧和烧结蜂窝多孔材料、抗菌材料载体、赤泥脱硫与固硫材料、赤泥用于炼铁氧化球团黏结剂等研究新进展。对赤泥进行减量化、资源化利用不仅能减少其对环境污染,还可缓解我国铝土矿资源短缺等问题。     

烧结法赤泥的强度演化规律

筑坝堆存是现在处理赤泥的主要方式,为了堆场安全继续向上堆载,对烧结法赤泥强度的演变规律进行了研究。通过对比不同深度处赤泥的抗剪强度,表明赤泥强度的形成与堆载时间没有必然的联系;再通过对新进场的赤泥进行强度追踪,得到赤泥强度形成过程中抗剪强度与滤水固结时间的关系曲线,从时间因素上为赤泥的安全堆载提供一个理论依据。     

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。     

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。     

赤泥的土壤化改良研究进展综述

赤泥是氧化铝生产过程中产生的固体废弃物，年产量和堆存量大，理化性质极端，严重威胁赤泥堆场周边生态环境和居民健康。赤泥土壤化改良和堆场生态修复被认为是最有希望解决赤泥问题的方法之一。对赤泥的基本理化性质，赤泥土壤化改良机理、改良措施(基质改良、植物修复和微生物修复等)及其存在问题、改良过程中的潜在生态环境风险等进行了研究和总结分析，并对赤泥土壤化改良领域未来的研究工作进行了展望和建议。     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.