气相色谱法测定禽蛋中微量有机氯农药及多氯联苯的残留

建立了以正己烷振荡提取，以及PCB2和PCB209为内标的快速检测禽蛋中微量有机氯污染物的气相色谱法。与传统的索氏提取法相比，在保证足够的准确度，精确度和灵敏度的前提下，具有前处理简单，测试成本低，标本用量少的特点。而且可同时测定有机氯农药和典型的多氯联苯类化合物的残留，特别适于检测食品中的微量有机污染物。用该方法测试的结果表明，标准全蛋粉添加ng/g级待测物时，各种待测物的回收率为84．31％－116．77％（3次测定平均值）；相对标准偏差为6％－18％（7次测定平均值）；最低检出量为0.07ng/g-0.35ng/g。中国部分城市市售鸡蛋中的有机氯农药以p,p'-DDE的检出量最高，p,p'-DDT次之；多氯联苯的检出量很低，大多数样品中多氯联苯的总检出量低于10ng/g。在所检出的多氯联苯中，绝大部分为含氯低的（氯原子数为3－5）的氯化物。     

Randomly Methylated β-Cyclodextrins (RAMEB) Enhance the Aerobic Biodegradation of Polychlorinated Biphenyl in Aged-Contaminated Soils

The biological removal of polychlorinated biphenyls (PCBs) from contaminatedsoils is adversely affected by the poor bioavailability of these pollutants. Twodifferent aged-contaminated soils containing about 890 and 8500 mg/kg of PCBswere supplemented with biphenyl and treated in slurry- and solid-phase aerobic0.5 litre-microcosms in the presence of RAMEB at 0, 0.5, 1.0, 3.0% (w/w). RAMEB,which was non-toxic and slowly biodegraded by the soil microorganisms, significantlyenhanced the bioavailability (from 30 to 50%) and the biological degradation (from 15to 55%) and dechlorination of PCBs in both soils and treatment conditions. RAMEBeffects were dependent on the concentration at which it was applied, the soil featuresand the treatment conditions. RAMEB enhanced PCB biodegradation by increasingboth the PCB bioavailability and the availability of biodegrading bacteria in themicrocosms. RAMEB appears a promising bioavailability enhancing agent for thetreatment of PCB-contaminated soils, not only for its positive effects on the PCBsbiodegradation, but also for its biodegradability, non-toxicity and relatively low cost.     

Speciation analysis to unravel the soil-to-plant transfer in highly arsenic-contaminated areas in Cornwall (UK)

Two areas near derelict calciners in Cornwall (UK) were chosen to study the uptake of arsenic from arsenic-contaminated soil into indigenous plants (heather, Calluna vulgaris; blackberry, Rubus ulmifulmus; gorse, Ulex europaeus). With total arsenic concentrations in soil ranging from 1240 to 2860 mg kg^?1 at Site 1 (Tuckingmill), no adverse effects on the growth of the plants studied were observed. Very low soil-to-plant transfer factors (0.01 to 0.03) were found although they were much higher when the extractable soil arsenic concentrations were taken into account (0.1 to 1.1). In the central dump area at Site 2 (Bissoe, 9.78% [w/w] arsenic in soil), the only plant to grow was heather, although it was severely impaired. However, heather was thriving at the edge of the dump where higher soil arsenic concentrations were found (10.32% [w/w]), indicating that arsenic is not a growth-limiting factor in itself. Soil-to-plant transfer factors in the range 2 × 10^?5–9 × 10^?4 confirm that arsenic is indeed effectively excluded from uptake, even taking into account extractable soil arsenic concentrations (9 × 10^?4–1.2 × 10^?2).

Extraction of bioavailable arsenic from soil using 0.05 mol L^?1 ammonium sulphate yielded recoveries from 1.18 to 3.34% of the total arsenic, predominantly in the form of arsenate. Extraction of arsenic and its metabolites from plants was achieved with water or a water/methanol mixture yielding recoveries up to 22.4% of the total arsenic, with arsenite and arsenate the predominant arsenic species and a minor fraction consisting of methylarsonic acid, dimethylarsinic acid and trimethylarsine oxide. The identity of the remainder of the non-extractable arsenic species still has to be revealed. Although the data suggest that higher plants synthesise organoarsenic compounds it cannot be excluded that symbiotic organisms have synthesised these compounds.     

Bioaccumulative Behaviour of Some PCB Congeners in Lake Geneva Brown Trout (Salmo trutta lacustris L)

Abstract

The bioaccumulation of PCBs has been studied for 60 Brown trout in Lake Geneva (Switzerland). The contamination level (1–3 ppm in wet weight, 10–30 ppm in lipid weight) is rather high.

Bioaccumulation curves (concentration as a function of the weight of the fish) have been established for 6 congeners and total PCBs. The total concentration of PCBs in wet weight increased with the weight of the fish; highly-chlorinated congeners (I.U.P.A.C. nr. 180, 2,3,4,5,2′,4′,5′-heptachlorobiphenyl) presented a faster, and lightly-chlorinated (I.U.P.A.C. nr. 28, 2,4,4′-trichlorobiphenyl) a slower, bioaccumulation tendency.

The total concentration of PCBs in lipid weight was constant, the concentration of congener 28 increasing and of congener 180 decreasing with the weight of the fish. This is attributed to the antagonistic effects of “growth and lipid dilution” and of the decrease of elimination kinetics as a function of the weight (and age) of the fish.

The partitioning theory and the pharmacokinetic approach are complementary methods for analysing this field data.     

Distribution and Assessment of Heavy Metals in Trifolium dubium (Little Hop Clover) and the Impact of Soil Quality

Trifolium dubium is an edible plant that is utilized in traditional medicine for its anti-inflammatory and wound-healing properties. In this study, T. dubium was assessed to determine the elemental uptake by the plant as a function of soil characteristics. Across 10 geographic locations in KwaZulu-Natal, South Africa, the concentration of elements in T. dubium were found to be (descending order) Ca?>?Mg?>?Fe?>?Zn?>?Mn?>?Se?>?Ni?>?Cr?>?Cu?>?Co?>?Pb?>?Cd?>?As. The site had an influence on elemental uptake by the plant; however, accumulation or exclusion of elements from soil was controlled to meet physiological requirements. Soil chemical characteristics showed T. dubium grew in slightly acidic soils (pH – 6.15 to 6.68). The findings of this study show T. dubium to contain adequate concentrations of essential elements with undetectable levels of toxic metals, making the herb safe for human consumption and for use in traditional medicine. The plant can also contribute to poor communities by ameliorating food insecurity.     

Using Surfactant System to Wash a Polluted Soil by Petroleum Derivatives in Egyptian Abu Madi Fields in Terms of Emulsification

The exploration and production activities of the natural gas in Abu Madi region (in middle delta) progressed in the last decade. The condensate hydrocarbon and formation water are bi‐products produced during the natural gas industry. The accompanied water contains 10–15% condensate (gasoline). This water with gasoline was drained into the Shehab El‐Din drain. The farmers were used this water to irrigate their fields. Great areas of the fields were out of order of planting as the result of gasoline pollution. This work concentrates on washing the polluted soil using locally prepared surfactant (LABSA‐Na) in the washing process. The soil sample was picked up from the Abu Madi field and was divided into pots (four pots for each treatment). The experiment was designed on the basis of polluting the soil by gasoline (condensate) from 1 to 10%. The washing process was carried out in presence of 0.1, 0.3, and 0.5% surfactant solutions. The control and blank sample were taken in consideration. The washed and the latent oil percentages were determined using the spectrophotometric method. After polluting and washing the soil, the pots were fertilized and planted by Zea Mays. The pots were irrigated twice a week. The length of plants was followed up. The obtained results cleared that, the efficiency of washing process increases with increasing of the pollutant percentage and also with increasing of surfactant concentration. The maximum washed oil (gasoline) was obtained at 10% gasoline and 0.5% surfactant concentration. The length of plants after 21 days of planting were; 0 (no planting), 24, 34, 39, 54, and 57 cm against polluted soil and planted (control) washed soil by water only; washed soil by 0.1%; washed soil by 0.3%; washed soil by 0.5% and no polluted soil (blank) respectively. These data revealed that, removing the hydrocarbon from the soil by washing using surfactants is the most effective method as the result of solubilization and emulsification of the hydrocarbon by surfactant which make it more removable.     

A Thermogravimetric Approach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid)

Summary: An amorphous grade Poly (lactic acid) (PLA) was selected for an accelerated burial in soil test during 450 days. Thermogravimetric analyses were carried out to study the effects of degradation in soil on the thermal stability and the thermal decomposition kinetics. A single stage decomposition process is observed for all degradation times. It is shown that the thermal stability of PLA is slightly affected by degradation in soil. Concerning the study of the thermal decomposition kinetics, Criado master curves were plotted from experimental data to focus the study of the thermodegradation kinetic model.The kinetic methods proposed by Broido and Chang were used to calculate the apparent activation energies (Ea) of the degradation mechanism. These results were compared to the Ea values obtained by the method developed by Coats and Redfern in order to prove the applicability of the former methods to the kinetic study. As expected, non-linear tendency is found out for Ea variation along the degradation times, which can be explained as an evolution by stages.     

Possibility of New Active Substrates (ASs) to Be Used to Prevent the Migration of Heavy Metals to the Soil and Water Environments

This paper aims to propose an alternative to the known permeable reactive barriers (PRBs). PRB is one of the methods, which is a reactive barrier placed below the ground, to clean up contaminated groundwater. New polymer active substrates (ASs) were used to prevent soil contamination by toxic heavy metals. The active substrates consisted of a mixture of poly(vinyl chloride), Aliquat 336, and bis(2-ethylhexyl)adipate, which was applied to the skeleton material (fiberglass or textile). Aliquat 336 was used as a binding agent for metal ions (Cr(VI), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II)). In contrast with the PRBs, the ASs (from AS-1 to AS-5) were obtained in a simple way using the pouring method. The obtained ASs could be recycled and reused. The active substrates were used for the binding of various metal ions from aqueous solutions and the examined soil. It was found that the active substrate AS-1 decreased the concentrations of nickel, cadmium, and lead by more than 50% and that of chromium by more than 90% in the aqueous solution. High sorption efficiency for chromium and zinc metals (81% and 66%) with the use of AS-2 was also found, owing to which the migration of metals from soil to water can be limited. In the soil environment, active substrate AS-5 with the addition of a plasticizer showed the greatest effectiveness. This solution resulted in a reduction in each tested metal ion of at least 50%, and reductions in cadmium, lead, and copper of over 70%.     

新型除草剂双甲胺草磷(H-9201)在胡萝卜和土壤中的残留动态研究

建立了新型除草剂双甲胺草磷(H-9201)残留GC FPD检测方法,并对其在胡萝卜田的残留动态进行了研究.结果表明:植物样本的平均添加回收率为89.2%～101.8%,变异系数为:4.3%～5.0%,土壤中的平均添加回收率为90.8%～95.1%,变异系数为:3.0%～16.4%.本方法对双甲胺磷的检出限为:胡萝卜中为0.01 mg/kg,土壤中为0.005 mg/kg.残留动态研究表明:双甲胺草磷土壤中的半衰期为27.8 d,胡萝卜中的最终残留量＜0.02 mg/kg,土壤中的最终残留量＜0.4 mg/kg.     

Some Considerations with Regard to the Quality of Results of Analysis of Trace Element Extractable Contents in Soil and Sediment

Abstract

Attention is drawn to the necessity to demonstrate accuracy of analytical results in order to make them comparable with results obtained elsewhere in the world. Besides the general aspects of quality management (e.g. within and between laboratories), attention is paid to the pitfalls that may occur in soil and sediment extract analysis. Especially the practical aspects of calibration are being dealth with.     

便携式激光诱导击穿光谱仪测定土壤中重金属

土壤重金属污染对农作物生长和人体健康都有严重危害,现场快速检测对土壤重金属污染调查、应急监测具有重要意义。采用自主研发的土壤重金属激光诱导击穿光谱现场快速检测仪对矿区周边土壤进行现场检测分析,以835个不同基质土壤的光谱数据建立定标数据库,通过支持向量机建立回归模型对土壤重金属元素含量进行定量反演。现场检测获取的全波段光谱波动在15%以内,Cd、Cr、Cu、Ni、Pb和Zn等6种元素光谱强度相对标准偏差平均值为6.31%。将检测结果与实验室电感耦合等离子体质谱法分析对比,6种元素的皮尔逊相关系数r在0.850 1～0.982 9,检测结果80%以上处于±30%相对误差区间分布。对比结果表明自主研发的土壤重金属激光诱导击穿光谱现场检测仪可以满足现场快速检测需求。     

羰基钴催化烯烃醛化反应中RCOCo(H)2(CO)3还原消去关键步骤的理论研究

在其催化循环过程中,RCOCo(CO)_3与H2_氧化加成生成RCOCO(H)_2(CO)_3,此中间体进一步还原消去生成醛是涉及氢在整个醛化反应催化循环中活化作用的关键步骤,文献[2]认为它是整个循环的控制步骤,由于反应的各中间物光谱无法准确测定,无法分别考察这两个步     

The use of iminopyridines as efficient ligands in the palladium(II)-catalyzed cyclization of (Z)-4′-acetoxy-2′-butenyl 2-alkynoates

Iminopyridines were found to be a sort of efficient bidentate ligands for the palladium(II)-catalyzed cyclization of (Z)-4′-acetoxy-2′-butenyl 2-alkynoates in acetic acid to afford the α-(Z)-acetoxyalkylidene-β-vinyl-γ-butyrolactones. The iminopyridine ligands could not only inhibit β-hydride elimination but also stabilize the vinyl-palladium intermediate in acetic acid in the reaction.     

Speciation Determination of Chromium(VI) and Chromium(III) in Soil Samples after Cloud Point Extraction

Abstract

To measure the different activity of chromium(VI) and chromium(III) in soil samples, chromium(VI) and total chromium (CrVI + CrIII) was extracted by KCl extracting agent and alkali fusion, respectively. Cloud point extraction (CPE) for speciation determination of chromium with double-slotted quartz tube atom trap–flame atomic absorption spectrometry (STAT-FAAS) was developed. Preconcentration of chromium(VI) and total chromium in different pH solutions was achieved by CPE, with ammonium pyrrolidine dithiocarbamate (APDC) as the chelating agent and Triton X-114 as the cloud point extractant. The conditions of CPE and determination were studied. Under the optimal conditions, the enrichment factor was 50 for chromium from the initial 100-mL sample solution to the final 2-mL determined solution. Compared to the FAAS method, the sensitivity was improved seven-fold for chromium by the STAT-FAAS method. The limit of detection was 0.082 µg/L for chromium.     

Foliar Spray with Pepsin-and Papain-Whey Protein Hydrolysates Promotes the Productivity of Pea Plants Cultivated in Clay Loam Soil

Papain and pepsin-hydrolyzed whey protein (PAH and PEH, respectively) were prepared and characterized for its degree of hydrolysis, chemical constituents (amino acid and peptides) and antioxidant activity. A field experiment was conducted at El Salheya El Gedida City, Sharqia, Egypt, during the seasons 2019 and 2020, to investigate the biological action of the foliar spray of PAH and PEH on the growth and yield of pea plants cultivated in a clay loam soil. Foliar application of the papain and pepsin-hydrolyzed whey protein (PAH and PEH, respectively) at 1000 and 2000 mg/L was applied three times after 25, 35 and 45 days from planting. All protein foliar spray treatments had significant positive effects on the uptake of N, P and K, simultaneously increasing the contents of all the photosynthetic pigments (Chlorophyll a, Chlorophyll b and Carotenoids) in a concentration-dependent manner. The most conspicuous increase was seen in Chlorophyll b (105% increase), followed by Carotenoids (91% increase). Generally, the favorable increases caused by the second level of application (2000 mg/L) were nearly 2–3 times that of the low level (1000 mg/L). Pod growth and formation indicators, e.g., no. of pod/plant, pod length and no. of seeds/pod, responded more evidently to the hydrolyzed than the intact form of whey protein treatments. Hydrolyzed whey protein foliar spray treatments achieved significantly higher increases in the global field yield components of Pisum sativum plants than the intact form, where peptic hydrolysates were significantly superior to papain hydrolysate. The treatment PEH (2000 mg/L) can be recommended as the most effective bio-stimulating foliar spray treatment for higher plant productivity when applied 25, 35 and 45 days after planting.     

粗径毛细管气相色谱法测定F8426在土壤和小麦中的残留量

 用气相色谱法测定了快灭灵 40 %干悬浮剂中F842 6在土壤和小麦中的残留量。用丙酮 水 (体积比为 80∶2 0 )溶液提取土壤和小麦样本中的F842 6 ,然后用石油醚萃取。石油醚相经浓缩后过弗罗里硅土和活性炭 (0 97g +0 0 3g)混合小柱净化 ,再用OV 170 1粗径毛细管柱分离 ,用电子捕获检测器 (ECD)测定。该方法对F842 6的最小检出量为 0 0 2ng ,在小麦和土壤中F842 6的最低检出限分别为 2 μg/kg和 1μg/kg ,对土壤和小麦空白样本的平均添加回收率为 89 6 0 %～ 97 5 3%,变异系数为 4 42 %～ 8 6 7%。。     

添加有机肥和葡萄糖对铜毒害旱地红壤微生物生物量的影响

在预培红壤中加入定量的有机肥和葡萄糖及不同浓度的Cu,25℃培养14d，测定了土壤微生物生物量C（Cmic),N(Nmic)。结果表明，存在有机肥和葡萄糖时，土壤中Cmic和Nmic随着Cu浓度的增加而降低；Cmic/Nmic随着Cu浓度的增加而增大。施加有机肥和葡萄糖的土壤中，在所有Cu处理浓度下，土壤中Cmic和Nmic均比未加有机物质处理高，特别是有机肥处理中土壤Cmic和Nmic均比其它处理高得多，说明有机肥可明显减轻Cu对土壤微生物生物量的毒性，同时也说明有机肥可提供微生物N源。不含Cu时，加入有机肥和葡萄糖导致土壤中Cmic和Nmic增加，其中有机肥明显。     

Elemental Analysis of Edible Mountain Nettle (Obetia tenax) and the Influence of Soil on Its Chemical Composition

In developing countries, the dietary intake of essential elements is largely dependent on the consumption of edible fruits and leafy vegetables. The distribution of elements in the indigenous edible plant, Obetia tenax (mountain nettle), was investigated as a function of soil quality from eight sites in KwaZulu-Natal, South Africa. The results show concentrations of elements in the leaves to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?>?Cr?>?Cu?>?Ni?>?Pb?>?Co?>?As?>?Cd?>?Se, and in the stems and roots to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?>?Cu?>?Ni?>?As?>?Pb?>?Co?>?Cd?>?Cr?>?Se. The quality and pollution status of soil was evaluated by geoaccumulation indices and enrichment factors, which indicated moderate cadmium contamination at the Msinga location that was confirmed by the pollution index and ecological risk levels of single-factor pollution. An assessment of overall contamination of soil using Nemerow pollution index showed moderate pollution by cadmium, while the potential toxicity index indicated low-grade risk for all elements at all sites. Principal component and cluster analysis revealed two groups of elements with similarities, As, Cd, Co, Cr, Cu, Mn, Ni, and Fe, suggesting a lithogenic source and an anthropogenic source for Pb and Zn. Correlation analysis showed significantly positive correlations between As, Co, Cr, Cu, Fe, and Ni/Cd in the soil, confirming the elements’ common origin.