基于响应面法优化MAP法处理垃圾渗滤液工艺的研究

利用单因素实验以及响应面法(response surface methodology,RSM),对磷酸铵镁法(magnesium ammonium phosphate,MAP)去除垃圾渗滤液氨氮的影响因素进行了分析和探讨。考察了pH值为8.0～11.0、n(Mg)∶n(N)摩尔比为0.8～1.6、n(P)∶n(N)摩尔比为0.8～1.3条件下,分析氨氮去除率的变化,用Design-Expert软件处理实验数据,得到了二次响应曲面模型以及优化的水平值。基于经济和操作简便性的考虑,pH值由优化水平的8.3调整为9.5,n(Mg)∶n(N)、n(P)∶n(N)摩尔比取优化水平分别为1.40、1.19,氨氮去除率平均值为92.2%,虽然该条件比最佳条件下的氨氮去除率降低了2个百分点,但从操作的难易程度以及经济性方面,体现了其优势。通过X衍射与电镜扫描分析沉淀物质的成分与晶形,表明大部分沉淀物质为磷酸铵镁。     

嗜酸氧化亚铁硫杆菌脱煤矸石中硫影响因素的筛选及条件优化

采用Plackett-Burma(P-B)和Box-Behnken(B-B)设计相结合的方法筛选和优化嗜酸氧化亚铁硫杆菌(A.ferrooxidans)脱除煤矸石中硫的主要影响因素和实验条件。首先,通过P-B设计从pH、煤矸石粒度、煤矸石添加量、Ag+浓度和煤矸石类型等因素中筛选影响脱硫率的主要因素。然后,在确定使用新鲜矸石条件下,对另外4个主要因素采用BB设计和响应面分析进行脱硫条件优化。研究结果表明,pH、煤矸石粒度和Ag+浓度对脱硫率具有显著影响,其影响程度为煤矸石粒度pHAg+浓度。利用Design Expert软件建立起脱硫率与影响因素之间的二次回归方程模型,通过求解方程得到最优脱硫条件为pH(3.0)、煤矸石粒度(124μm)、煤矸石添加量(56 g/L)、Ag+浓度(100 mg/L),在该条件下实际脱硫率达88.62%,与模型预测值接近,说明可以利用该模型来分析和预测矸石的脱硫效果。     

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%。     

利用白云石回收污泥厌氧消化液中的磷

为经济有效地从污泥厌氧消化液中回收磷,构建了以白云石提供钙镁源的磷回收方法,探讨了磷回收的工艺条件与效果。通过盐酸酸化厌氧消化液以降低其碳酸盐含量,同时利用白云石溶于冷稀盐酸的特性使其钙镁缓慢释放到酸化的厌氧消化液中形成第一步磷回收体系,考察体系酸化pH、白云石与厌氧消化液的固液比以及反应pH对白云石的钙镁释放和磷回收效果的影响;第一步磷回收后的上清液为第二步厌氧消化液磷回收提供钙镁源,研究投加钙磷摩尔比对磷回收效果的影响。实验结果表明,当固液比为5.0时,在酸化pH为4.0～4.5且酸化溶出时间为10 h以及反应pH为9.0的条件下,第一步磷回收产物以磷酸钙盐沉淀为主,厌氧消化液磷回收率及回收产物含磷率（以P2O5计）分别达到99.43%和38.49%;第一步磷回收后的上清液按一定的钙磷摩尔比投加到酸化后的厌氧消化液中进行第二步磷回收,当投加钙磷摩尔比为0.20时,在反应pH为9.0的条件下,回收产物同时含有磷酸钙盐和磷酸铵镁,厌氧消化液中氮、磷回收率分别达到13.19%和90.90%,回收产物氮、磷含量（以P2O5计）分别为0.26%和39.58%;经XRD、XRF、ICP及SEM等分析表征,2步磷回收的产物以磷酸钙盐和磷酸铵镁为主要成分,杂质少。研究表明,利用白云石为钙镁源,通过分别构建不同的磷回收体系可以分步从污泥厌氧消化液中经济有效地回收磷,且磷回收率和回收产物含磷率高。     

含油污泥化学清洗处理实验研究与工艺参数优化

以大庆采油一厂的含油污泥为研究对象,采用化学清洗方法,以处理后底泥残油率为评价指标,优化影响含油污泥清洗效率的参数。根据单因素实验,确定清洗温度、化学药剂浓度、液固比的取值范围;采用Design-Expert响应曲面法,考察单独变量作用及交互作用对含油污泥残油率的影响。选择软件中二次多项式模型进行模拟可知,单因素变量、清洗温度与化学药剂浓度的交互项均对含油污泥残油浓度具有显著影响;模型优化结果显示,化学法处理含油污泥的最佳工艺条件为清洗温度78.68℃、化学药剂浓度0.84 g·L~(-1)、液固比9.40∶1,模型预测底泥残油率为3.85%,实验验证结果的平均值是3.96%,测定值与预测值之间相对误差为2.78%,证明该模型的可靠性。     

响应面分析法优化絮凝酵母SPSC01去除Cr(Ⅵ)

采用响应面法对絮凝酵母SPSC01去除水中Cr(Ⅵ)的条件进行优化。根据Box-Behnken Design的中心组合实验设计原理,采用三因素三水平的响应面分析方法,优化絮凝酵母SPSC01对Cr(Ⅵ)的去除。二阶模型的方差分析表明,预测响应值和实际值相符合,针对初始浓度为50 mg/L的Cr(Ⅵ)废水,在絮凝酵母SPSC01用量为10.89 g/L干重、温度为40℃、初始pH为2时的去除条件最优,二阶模型分析预测絮凝酵母SPSC01在4 h时对Cr(Ⅵ)去除率可达95.47%,在此条件下,实测Cr(Ⅵ)的去除率达93.06%,说明利用响应面法优化絮凝酵母SPSC01对Cr(Ⅵ)的去除条件是可行的。     

酸浸法提取煤矸石中Al2O3的研究

煤矸石是主要的煤系固体废物,其中Al2O3质量分数约占35％左右.以某煤矿的煤矸石为原料,通过单因素实验比较盐酸和硫酸对Al2O3的浸取率,研究各因素对Al2O3浸取率的影响,确定浸取煤矸石中Al2O3的最佳酸浸介质为硫酸.利用正交实验确定酸浸取的最佳条件为:液固比(酸溶液体积与煤矸石样品质量比)15 mL/g、硫酸摩尔浓度3 mol/L、浸取时间120min、助样比(助溶剂与煤矸石样品质量比)0.20,在此条件下硫酸对煤矸石中A12O3的浸取率可达79.6％.     

剩余污泥水解酸化液中营养元素与有机质的回收

为回收剩余污泥水解酸化液中的营养元素与有机质,构建了白云石-水解酸化液钙镁溶出体系,获得富含钙镁的溶出液,控制溶出液反应pH和反应时间进行第1阶段回收,以回收后的上清液进一步作为钙镁源从水解酸化液中进行第2阶段回收。结果表明,钙镁溶出的适宜条件为酸化pH 4.0~4.5、白云石颗粒50~80目、固液比3∶100(每100mL水解酸化液中投加3g筛分后白云石)、溶出时间10h;第1阶段回收适宜的反应pH为8.5,氮(以氨氮计)回收率、磷(以可溶性正磷酸盐(以P计)计)回收率分别为10.24%和95.89%;第2阶段回收适宜的镁磷摩尔比为0.60、反应pH为9.0,此时氮、磷回收率分别为14.60%和83.91%;傅立叶红外变换(FTIR)和电感耦合等离子直读光谱(ICP)分析表明,回收产物主要由无机养分和有机质组成,重金属含量极少。利用白云石提供钙镁源能经济有效地回收剩余污泥水解酸化液中的氮、磷等营养元素,同时回收有机质,回收产物品质符合《有机-无机复混肥料》(GB 18877—2009)中Ⅰ型肥料要求。     

树空坪矿区磷矿废石磷素的浸出特性

研究不同液固比条件下磷矿废石磷素浸出特性,为磷矿废石利用及治理提供理论依据和技术指导,进行磷矿废石磷素静态淋溶实验。结果表明:磷矿废石磷素释放过程中,液固比直接影响磷矿废石中磷素释放速率;低液固比条件下(液固比小于5.0 m L·g~(-1)),固相和液相传质过程未达到平衡,溶液与磷矿废石相互作用在快速进行,高液固比条件下(液固比大于5.0 m L·g~(-1)),固相和液相传质过程趋于稳定;液固比淋溶实验过程中总磷浓度没有明显变化,而磷素累加释放量随着液固比呈现出线性变化,说明pH浸提液对于磷矿废石中磷素释放作用属于溶解度控制。     

燃煤电厂粉煤灰中汞的稳定性研究

燃煤飞灰中高度富集了痕量元素汞,而汞具有易挥发特性、较强的毒性和不易降解等特点,在粉煤灰的利用过程中汞极易逸出,造成二次污染,对人体健康有极大危害,所以对燃煤飞灰中汞稳定性的研究具有重要的意义。通过模拟加工利用和储存的自然环境,对飞灰和漂珠进行煅烧实验,研究飞灰和漂珠中汞的含量与煅烧温度之间的关系;对飞灰进行浸取实验,研究飞灰中汞的含量受浸取液pH以及浸取时间的影响情况。结果表明:在煅烧实验中,煅烧温度是影响汞释放的主要原因,随煅烧温度的增加汞的流失量越大,随煅烧时间的延长汞的流失量越大,在相同煅烧温度(500℃)和不同煅烧时间条件下,飞灰中汞的流失率最高达98.5%,漂珠中汞的流失率最高达86.4%,在相同煅烧时间和不同煅烧温度条件下,飞灰中汞的流失率最高达97.8%,漂珠中汞的流失率最高达85.7%;在浸取实验中,浸取时间越长,汞的流失量越大,当浸取液pH为1、浸取时间24h时,飞灰中的汞由0.331 8μg/g降低至0.137 1μg/g,说明浸取时间越长,汞浸出率越高,在不同pH条件下,汞含量随pH的降低而减少,飞灰中汞的浸出率最高达58.7%,最低为15.7%。     

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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

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.     

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

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

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.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

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.