湿法回收砷碱渣中锑的工艺研究

本研究先以水浸实现砷碱渣中的砷锑分离，再对水浸渣进行盐酸浸出，得到了可作为工业原料氯化锑溶液。研究结果表明，在液固比为6：1，温度40℃，浸出时间40min的条件下，可使水浸过程中锑的浸出率低于3％，砷的浸出率达到99％；盐酸浸出中，控制酸浓度为1：1，液固比10：1，温度60℃，授出时间30min，能使锑的浸出率达到88％以上。经过水浸和盐酸浸出，锑的直接回收率为85．36％。     

响应曲面法优化炼铅高砷烟尘的浸出工艺

考察炼铅高砷烟尘中砷在水中的浸出行为。采用响应曲面法常用的中心复合设计对液固比、温度和时间工艺参数进行优化研究。结果表明,温度对砷浸出率的影响最大,时间次之,液固比最小。通过响应曲面法优化得到的最佳浸出工艺为:液固比=14∶1,温度85℃,时间120 min。该条件下3次验证实验的砷浸出率平均值为89.64%,与预测值89.88%无显著差异,表明所建模型切实可行。烟尘经过二次水浸后砷的总浸出率达到98.1%。     

盐酸浸出提取赤泥中铝和铁的工艺条件优化

系统研究盐酸浸出赤泥中铝和铁的过程,考察酸浸温度、盐酸浓度、酸浸时间、液固比以及赤泥粒度对铝、铁浸出率的影响。单因素实验和正交实验结果得出,在影响浸出率的酸浸温度、盐酸浓度、酸浸时间和液固比对铁、铝的浸出率的影响几个因素中,酸浸温度和盐酸浓度的影响最大,液固比和浸出时间其次。盐酸酸浸的最佳工艺条件为:赤泥粒度150μm、酸浸温度80℃、盐酸浓度10 mol·L~(-1)、液固比8∶1(V/m)、浸出时间150 min,此时铝的浸出率为96.7%,铁的浸出率为95.1%,铁铝总浸出率96.0%。     

盐酸分级浸出赤泥中有价金属元素

采用盐酸2段分级浸出工艺回收氧化铝赤泥中的有价金属元素。通过考察液固比、反应温度、反应时间及盐酸使用量对浸出率的影响,确定了2段浸出的实验工艺。结果表明:在盐酸用量为理论用量的40%、90℃液固比为7∶1、反应时间1 h的条件下,Ca的浸出率为96.2%,Na的浸出率为82.47%,Al的浸出率为42.87%,其他元素几乎不浸出,这是第1段浸出;在盐酸用量为理论量的130%、90℃、盐酸浓度8.8 mol·L~(-1)的条件下,浸出1段酸浸渣,Fe的浸出率99.65%,Sc的浸出率88.76%,V的浸出率93.58%,其他稀土元素的浸出率均达到了70%左右,这是第2段浸出。     

氧化氨浸工艺回收硫化砷渣中的铜

对在(NH4)2S2O8-NH3-H2O体系中氧化浸出硫化砷渣(砷渣)中的铜进行热力学分析;讨论了浸出温度、c(NH3)/c(NH+4)、液固比、浸出时间及总氨浓度对铜浸出率的影响,确定了从砷渣中回收铜最佳浸出工艺条件;采用XRD和SEM对浸出渣进行表征。结果表明,氧化氨浸回收铜工艺具有热力学可行性;在浸出温度35℃,c(NH3)/c(NH+4)1∶7,液固比6∶1,浸出时间3 h,总氨浓度4 mol/L的条件下,铜的浸出率为70.74%;大量S0均匀分布在浸出渣中。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

氢氧化钠浸出氧化锌渣中的锌

在资源日益枯竭的现状下研究氧化锌渣的资源化回收利用具有较大的意义。对氧化锌渣碱性浸出影响因素浸出时间、浸出转速、浸出温度、浸出碱液的浓度和浸出的液固比等的研究,进行了浸出渣的物性表征,分析了主要的物相组成。研究结果表明,锌的浸出率最大为89.5%时,浸出条件为:浸出时间为120 min,浸出温度为75℃,浸出转速为250 r·min~(-1),浸出时氢氧化钠浓度为5 mol·L~(-1),液固比(体积质量比)为15∶1。渣中锌主要以氧化锌的形式存在。     

微波作用下氧化碱浸铜冶炼烟灰脱砷的动力学

采用微波氧化辅助Na2S-Na OH浸出体系对铜冶炼烟灰(简称"烟灰")进行研究。结果表明:当温度60℃,Na OH和烟灰的投加量比例为5 g∶10 g,Na2S和烟灰的投加量比例为8 g∶10 g,固液比为1∶20时,砷的浸出率为98.45%。动力学研究表明:砷的浸出过程在313~343 K内符合"未反应收缩核"模型,浸出过程受未反应核周围残留固体膜层扩散控制,经拟合得出浸出动力学方程,浸出表观活化能Ea=13.46 k J·mol-1。     

拜耳赤泥中镓的酸法浸出及残渣的除氟

贵州铝土矿资源普遍富含镓元素,拜耳法工艺中,约70%的镓随氧化铝同时溶出,其余30%残存于赤泥中未回收直接外排,造成镓资源的严重浪费。采用酸法工艺浸出拜耳赤泥中镓金属,设计4因素3水平L_9(3~4)正交实验,考察盐酸添加量、浸出温度、浸出时间和液固比对镓浸出效果的交互影响规律,并测试了浸出残渣对含氟水处理性能。结果表明:影响镓浸出率因素的主次顺序依次为盐酸添加量、浸出温度、液固比和浸出时间;最适宜浸出条件为盐酸过量系数1.2,浸出温度70℃,浸出时间3 h,液固比8 m L·g~(-1);该条件下,镓的浸出率为94.92%,浸出溶液含Ga 3.91 mg·L~(-1);除氟实验得出最佳除氟条件为,残渣添加量25 g·L~(-1),p H=4.7,接触时间6 h,旋转速率200 r·min~(-1);室温下进行3组平行实验,平均除氟率为57.54%,表明浸出残渣具有一定的除氟性能。     

含砷冶炼废渣高温烧结过程砷的迁移特性

研究了烧结温度和烧结时间对含砷冶炼废渣烧结过程中砷的迁移特性的影响。烧结条件为在10 MPa下加压成型,进空气流量为2 000 mL/min,烧结温度1 000～1 350℃,烧结时间5～120 min。结果表明,烧结过程中存在砷的挥发,但烧结前后砷的总量变化不大,砷的固化率均保持在90%以上。毒性浸出实验表明,不同的烧结条件对烧结体中砷的毒性浸出有重要的影响,从烧结体的环境安全性考虑,最佳的烧结温度和时间分别为1 200℃和45 min。     

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.     

利用硫酸渣生产铁精粉的新工艺研究

实验了一种新的工艺来处理硫酸渣,该方法能很好地脱除烧渣中的硫并富集其中的铁,解决了硫酸渣脱硫难的问题。经过处理后可以将其开发为有用的铁精粉作为炼铁原料或者是生产其他铁系产品,实现了废物的资源综合利用。     

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.     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

Optimization and validation of enzyme-linked immunosorbent assay for the determination of endosulfan residues in food samples

In this study, an enzyme-linked immunosorbent assay (ELISA) was optimized and applied to the determination of endosulfan residues in 20 different kinds of food commodities including vegetables, dry fruits, tea and meat. The limit of detection (IC₁₅) was 0.8 μg kg^?1 and the sensitivity (IC₅₀) was 5.3 μg kg^?1. Three simple extraction methods were developed, including shaking on the rotary shaker at 250 r min^?1 overnight, shaking on the rotary shaker for 1 h and thoroughly mixing for 2 min. Methanol was used as the extraction solvent in this study. The extracts were diluted in 0.5% fish skin gelatin (FG) in phosphate-buffered saline (PBS) at various dilutions in order to remove the matrix interference. For cabbage (purple and green), asparagus, Japanese green, Chinese cabbage, scallion, garland chrysanthemum, spinach and garlic, the extracts were diluted 10-fold; for carrots and tea, the extracts were diluted 15-fold and 900-fold, respectively. The extracts of celery, adzuki beans and chestnuts, were diluted 20-fold to avoid the matrix interference; ginger, vegetable soybean and peanut extracts were diluted 100-fold; mutton and chicken extracts were diluted 10-fold and for eel, the dilution was 40-fold. Average recoveries were 63.13–125.61%. Validation was conducted by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The results of this study will be useful to the wide application of an ELISA for the rapid determination of pesticides in food samples.     

Detection of herbicides in water bodies of the Samambaia River sub-basin in the Federal District and eastern Goiás

Abstract

The objective of this study was to identify and quantify herbicide residues in water samples of rain, cisterns, streams, ponds, springs, semi-artesian wells, dams and a river in the Rio Samambaia sub-basin in the Federal District and eastern Goiás. A total of 287 samples were collected from 20 farms in the sub-basin in the rainy (February, summer) and dry (August, winter) seasons in 2016. Aminomethylphosphonic acid (AMPA, a glyphosate metabolite), clethodim, chlorimuron-ethyl, diuron, fluazifop acid (a fluazifop-p-butyl metabolite and the active ingredient), haloxyfop acid (a haloxyfop-methyl metabolite and the active ingredient), imazamox, mesotrione, metsulfuron, nicosulfuron and pendimethalin were not identified in any water sample. In the rainy season, approximately 99% of the samples contained residues at least one of the evaluated herbicides; in the dry season (, 100% of the samples contained residues of at least one of the evaluated herbicides. When considering only detection frequency, metribuzin, atrazine, clomazone and haloxyfop-methyl were the main herbicides found in the water of the Samambaia River sub-basin. In turn, based on levels higher than the limit of quantification, the main compounds detected were atrazine, clomazone, haloxyfop-methyl and glyphosate. In both seasons, the highest relative concentrations of herbicides for the rainy and dry seasons were found in spring water, 25% and 56%, respectively, and dam water, 23% and 16%, respectively.     

工业废渣基除磷材料的静态吸附研究

研究了高效除磷材料（EPRC）对磷素的吸附特性，考察了投加量、初始浓度、初始pH值、粒径等对EPRC吸附性能的影响，分析了不同条件下EPRC的吸附过程。结果表明，最佳投加量为3.5 g/250 mL时，去除率达91.07%，出水TP浓度为0.45 mg/L。随着粒径减小，EPRC对磷素的吸附量增大，吸附平衡时间缩短。溶液初始pH值在碱性条件下，吸附容量变大。     

废弃植物中药渣的热解特性及动力学研究

采用热重分析法(TGA)对丹参中药渣的热解特性及其动力学规律进行了研究。分析了不同升温速率(10、30和50℃/min)和不同粒径(0.85~0.6、0.3~0.18和0.125~0.1 mm)药渣的热解特性。结果表明,药渣热解可分为3个阶段:预热干燥阶段、主热解阶段和碳化阶段,随升温速率的升高,热重(TG)和微分热重(DTG)曲线向高温侧移动,药渣的最大失重速率也显著增加;与大颗粒相比较小颗粒的挥发分产量较大。采用Coats-Redfern法和Flynn-Wall-Ozawa(FWO)法对药渣热解的动力学进行分析,选出了较为合理的机理函数,并计算得出药渣热解活化能为62~72 kJ/mol。