高锰酸钾生产废渣中的高价锰回收方法研究

高锰酸钾生产过程所产生的废渣中含有较多的高价态锰,导致锰资源的浪费和潜在的环境污染问题。采用葡萄糖-硫酸还原浸取法浸取高锰酸钾渣中的高价锰,实验探讨了葡萄糖用量、硫酸用量及浸取温度等因素对锰浸取率的影响,并研究了化学氧化法回收二价锰的工艺条件。结果表明,在葡萄糖与高锰酸钾渣质量比为0.3、硫酸物质的量与高锰酸钾渣质量之...     

针对含砷硫酸烧渣酸浸液的铁盐沉淀固砷

为考察含砷硫酸烧渣中酸浸脱砷效果和铁盐沉淀固砷行为,采用常温常压酸浸法脱除硫酸烧渣中的砷,并对进入浸出液中的砷以铁盐沉淀的形式脱除,进而对沉淀渣的浸出毒性进行研究。同时,研究了磨矿细度、酸浓度、固液比、浸出时间对硫酸烧渣中砷脱除效率的影响。结果表明,通过控制浸出参数可以将硫酸烧渣中砷的质量分数降低到0.2%以下,通过调节浸出液的pH和Fe/As摩尔比将其中的砷以沉淀的形式脱除。当Fe/As 2、pH=4～6时,溶液中砷浓度降到了0.5 mg·L~(-1)以下。沉淀砷渣主要是以非晶态的形式存在,提高铁砷比有利于提高砷渣稳定性,从而降低浸出毒性。在Fe/As=3、pH=6.04～6.22的条件下,得到的沉淀渣的浸出毒性为0.711 mg·L~(-1)。因此,通过酸浸脱除硫酸烧渣中的砷,进而采用铁盐沉淀的方法能够实现硫酸烧渣中砷的安全处置。     

铬渣酸溶性六价铬浸出动力学研究

考察了铬渣中的六价铬的在硫酸中浸出行为,分别研究了温度、硫酸浓度和铬渣粒径对酸溶性六价铬浸出的影响.研究表明,酸溶性六价铬酸浸为化学反应过程,可用"颗粒不变缩核收缩芯模型"进行描述,通过尝试法,确定酸溶性六价铬浸出过程为内扩散控制类型,表观活化能为9.32 kJ/mol;在此基础上,经多元回归分析,得到了表观反应速率常数关于温度、硫酸浓度和铬渣粒径的经验表达式.     

硫铁矿烧渣制备无机复合混凝剂聚合铁盐

对用硫铁矿烧渣制备无机复合混凝剂聚合铁盐进行了试验研究,考察了影响烧渣酸溶和铁聚合的因素。结果表明,硫酸浓度、反应时间和体系温度等是影响硫铁矿烧渣中铁溶出率的主要因素,在烧渣液溶过程中添加适当的助溶剂,不仅能够加快酸浸速度,而且还可以提高产品的混凝性能。     

电解锰渣中锰的浸出条件及特征

采用水洗-酸解法回收电解锰渣中锰,探讨了清水量、酸量以及温度在不同阶段对锰浸(洗)出条件的影响,分析了回收锰的主要因素及浸出特征。实验结果表明,50 g电解锰渣经m渣∶m水=1∶10的清水水洗后,采用10%的硫酸在70℃的水浴温度下酸解2 h,Mn2+浸出量为1.673 g,回收率达到97.3%,而温度和酸度对锰离子的浸出影响明显,酸度调控可有效分离酸浸锰液中金属成分,为减少电解锰渣环境污染的同时,实现电解锰渣资源化利用。     

铬渣的热解无害化处理

采用热解工艺无害化处理铬渣,探讨了稻秆在铬渣无害化处理中的作用.研究了热解温度、稻秆与铬渣质量比、铬渣粒径及保温时间对铬渣热解无害化处理的影响,并分析了热解前后热解产物中铬元素形态的变化.结果表明,热解工艺能有效地将铬渣中Cr(Ⅵ)还原,稻秆热解过程中产生的气相挥发分对Cr(Ⅵ)的还原起核心作用.较为适宜的热解条件:热解温度为400 ℃,稻秆与铬渣质量比为0.10,铬渣粒径<2 000 μm,保温时间为10 min.在该热解条件处理下,热解产物中的Cr(Ⅵ)质量浓度为121 mg/kg,低于热解前铬渣中的Cr(Ⅵ)(3 400 mg/kg).热解后,可交换态及碳酸盐结合态铬含量降低,大部分铬转化成了稳定的有机结合态和残渣态,极大地降低了铬渣的危害.第一作者:张大磊,男,1982生,博士研究生,研究方向为固体废弃物热处理.     

林可霉素菌渣与牛粪联合堆肥实验研究

抗生素菌渣因含有抗生素残留而成为一种较难处理的废弃物,不合理的处理方法极易造成环境污染和生态危害,同时也会造成资源浪费.为了探讨林可霉素菌渣堆肥化处理的可行性,设计了林可霉素菌渣与牛粪的联合堆肥实验.4个堆肥处理的林可霉素初始含量分别为1.35 mg/g(干重)、1.89 mg/g(干重)、3.52 mg/g(干重)和...     

电解锰渣的综合利用进展与研究展望

电解锰渣是电解金属锰时产生的酸性滤渣,含有大量有害物质。随着电解锰行业的快速发展,大量堆放填埋的电解锰渣引发了严重的水土、生态环境污染问题,对锰渣的无害化处理与资源化利用已成为电解锰行业和环保领域的研究热点。在电解锰渣特性的分析基础上,对国内外电解锰渣的综合利用进展(如锰离子回收、肥料制作和建筑材料应用)进行了回顾,分析了锰渣各种资源化利用方法的优缺点。最后,展望了电解锰渣的研究与应用前景,旨在为锰矿资源的可持续性开发与电解锰渣的综合回收利用提供参考。     

高铁脱硫渣制备高纯度硫酸亚铁及草酸亚铁的研究

以高铁脱硫渣为原料，采取酸浸、除杂和结晶等工艺制备出99%以上硫酸亚铁晶体。研究了酸浸过程中硫酸浓度、浸取温度、时间对铁浸出率的影响，分析了各个影响因素的规律性。结果表明：适宜的浸取条件为硫酸溶液质量分数为25%，在70℃下，不断搅拌浸取6 h。固液分离后调节硫酸亚铁溶液pH=1～2，在70℃下蒸发浓缩结晶，即可得到99%以上硫酸亚铁晶体。     

水淬渣在稀土氨氮废水中的应用研究

研究了水淬渣原渣和铁改性水淬渣作为吸附剂处理稀土氨氮废水的工艺条件和吸附机理，实验表明，原渣和改性渣处理稀土氨氮废水的最佳反应时间都为60 min，原渣的最佳投加量为0.015g/mL，而改性渣的最佳投加量为0.01g/mL，原渣的氨氮去除率为(59.9±2.49)％，而改性渣的氨氮去除率为(79.24±1.21)％。...     

Immobilization of mercury by pyrite (FeS2)

Elemental mercury (Hg⁰) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.     

Potential sensitivity of mires to drought,acidification and mobilisation of heavy metals: the sediment s/(Ca + Mg) ratio as diagnostic tool

In recent decades sulphate concentrations in the ground water in many parts of The Netherlands have increased dramatically resulting in increased production of iron-(di)sulphides in sediments of ecosystems fed by this water. A sediment survey was carried out to study the potential sensitivity of wetlands to drought and subsequent acidification as a consequence of iron-(di)sulphide oxidation. Dessication led to severe acidification and mobilisation of heavy metals when the sediment S/(Ca + Mg) ratio exceeded 2/ 3. A total of 47% of the investigated locations contained S/(Ca + Mg) ratios higher than 2/3 and in 100, 75 and 50% of the locations mobilisation of Zn, Cd and Ni exceeded the Dutch signal value for ground water. Consistent with the sediment survey, lime addition experiments confirmed that increasing the buffer capacity, down to a S/(Ca + Mg) ratio 2/3, led to a drastic inhibition of the acidification and heavy metal percolation from dredged sediments. The performance of the same processes under drained field conditions demonstrates the relevance of these processes during dry summers.     

Impact of a proposed revision of the IESTI equation on the acute risk assessment conducted when setting maximum residue levels (MRLs) in the European Union (EU): A case study

ABSTRACT

Proposals to update the methodology for the international estimated short-term intake (IESTI) equations were made during an international workshop held in Geneva in 2015. Changes to several parameters of the current four IESTI equations (cases 1, 2a, 2b, and 3) were proposed. In this study, the overall impact of these proposed changes on estimates of short-term exposure was studied using the large portion data available in the European Food Safety Authority PRIMo model and the residue data submitted in the framework of the European Maximum Residue Levels (MRL) review under Article 12 of Regulation (EC) No 396/2005. Evaluation of consumer exposure using the current and proposed equations resulted in substantial differences in the exposure estimates; however, there were no significant changes regarding the number of accepted MRLs. For the different IESTI cases, the median ratio of the new versus the current equation is 1.1 for case 1, 1.4 for case 2a, 0.75 for case 2b, and 1 for case 3. The impact, expressed as a shift in the IESTI distribution profile, indicated that the 95th percentile IESTI shifted from 50% of the acute reference dose (ARfD) with the current equations to 65% of the ARfD with the proposed equations. This IESTI increase resulted in the loss of 1.2% of the MRLs (37 out of 3110) tested within this study. At the same time, the proposed equations would have allowed 0.4% of the MRLs (14 out of 3110) that were rejected with the current equations to be accepted. The commodity groups that were most impacted by these modifications are solanacea (e.g., potato, eggplant), lettuces, pulses (dry), leafy brassica (e.g., kale, Chinese cabbage), and pome fruits. The active substances that were most affected were fluazifop-p-butyl, deltamethrin, and lambda-cyhalothrin.     

Assisted phytoremediation of mixed metal(loid)-polluted pyrite waste: effects of foliar and substrate IBA application on fodder radish

Exogenous application of plant-growth promoting substances may potentially improve phytoremediation of metal-polluted substrates by increasing shoot and root growth. In a pot-based study, fodder radish (Raphanus sativus L. var. oleiformis Pers.) was grown in As-Zn-Cu-Co-Pb-contaminated pyrite waste, and treated with indolebutyric acid (IBA) either by foliar spraying (10 mg L⁻¹), or by direct application of IBA to the substrate (0.1 and 1 mg kg⁻¹) in association, or not, with foliar spraying. With the exception of foliar spraying, IBA reduced above-ground biomass, whilst direct application of IBA to the substrate surface reduced root biomass (−59%). Trace element concentrations were generally increased, but removals (mg per plant) greatly reduced with IBA application, together with greater metal leaching from the substrate. It is concluded that, in our case, IBA had a negative effect on plant growth and phytoextraction of trace elements, possibly due to unsuitable root indoleacetic acid concentration following soil IBA application, the direct chelating effect of IBA and the low microbial activity in the pyrite waste affecting its breakdown.     

Inflammatory stress response in A549 cells as a result of exposure to coal: Evidence for the role of pyrite in coal workers’ pneumoconiosis pathogenesis

On the basis of a recent epidemiological study it is hypothesized that pyrite content in coal is an important factor in coal workers’ pneumoconiosis (CWP) pathogenesis. While the role of pyrite in pathogenesis remains to be resolved, the ability of the mineral to generate reactive oxygen species (ROS) through various mechanisms is likely a contributing factor. The aim of this study was to elucidate the importance of the pyrite content of coal in generating an inflammatory stress response (ISR), which is defined as the upregulation of ROS normalized by cell viability. The ISR of A549 human lung epithelial cells in the presence of natural coal samples with variable pyrite contents was measured. Normalized to surface area, five particle loadings for each coal reference standard were analyzed systematically for a total of 24 h. The ISR generated by coals containing 0.00, 0.01, and 0.49 wt.% pyritic sulfur is comparable to,though less than, the ISR generated by inert glass beads (299% of the control). The coals containing 0.52 and 1.15 wt.% pyritic sulfur generated the greatest ISR (798% and 1426% of the control, respectively).     

Long term remediation of highly polluted acid mine drainage: a sustainable approach to restore the environmental quality of the Odiel river basin

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO₃ and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m³/day achieving an acid load reduction of 597 g·(m² day)⁻¹, more than 10 times higher than the generally accepted 40 g·(m² day)⁻¹ value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

土壤中结合态农药环境毒理研究进展

本文介绍了近年来国内外对土壤中结合态农药的研究动向,叙述了土壤中农药的结合残留量、环境意义及结合残留的分析测试技术,尤其对超临界流体萃取结合残留的技术作了介绍,并对该领域的深入研究提出了还需要解决的问题     

Impact of proposed changes in IESTI equations for short-term dietary exposure to pesticides from Australian and Codex perspective

ABSTRACT

In 2015 a scientific workshop was held in Geneva, where updating the four equations for estimating the short-term dietary exposure (International Estimated Short Term Intake, IESTI) to pesticides was suggested. The impact of these proposed changes on the exposure was studied by using residue data and large portion consumption data from Codex and Australia. For the Codex data, the exposure increased by a median factor of 2.5 per commodity when changing to the proposed IESTI equations. The increase in exposure was highest for bulked and blended food commodities (case 3 equations), followed by medium-sized food commodities (case 2a equations) and small- and large-sized food commodities (case 1 and case 2b equations). For the Australian data, out of 184 maximum residue limit (MRL) large portion combinations showing acute exposures below the acute reference dose (ARfD) with the current IESTI equations, 23 exceeded the ARfD with the proposed IESTI equations (12%). The percentage exceeding the ARfD was higher for the Australian MRL large portion combinations (12% of 184) than for those of Codex (1.3% of 8,366). However, the percentage MRL loss in the Australian dataset may not be representative of all pesticide MRLs since it concerns six pesticides only, specifically selected to elucidate the potential effects of the use of the proposed IESTI equations. For the Codex data, the increase in exposure using the proposed equations resulted in a small increased loss of 2.6% of the 1,110 MRLs estimated by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR): 1.4% of the MRLs were already not acceptable with the current equations, 4.0% of the MRLs were not acceptable with the newly proposed equations. Our study revealed that case 3 commodities may be impacted more by the proposed changes than other commodities. This substantiates one of the conclusions of the Geneva workshop to gather information on bulking and blending practices in order to refine MRL setting and dietary risk assessment for case 3 commodities where possible.