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。     

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。     

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%。     

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%。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.