A correlation between the biodegradability of oil products in the CEC L-33-T-82 and modified Sturm tests

Using a data set for 39 base oils, formulated oil products and pure compounds it was demonstrated that there was a good positive relationship between biodegradation in CEC L-33-T-82 and mineralisation to CO₂ in the modified Sturm test. A mathematical model was developed which described this correlation for most of the materials tested. One outlier from the model was di-iso tridecyl adipate (DITA), the well-degradable calibration oil for the CEC test. The measured mineralisation of DITA was much lower than that predicted by the model based on the compound's high biodegradability in the CEC test. A possible reason for this is given and the implications of this result discussed.     

An automated test for measuring polymer biodegradation

The biodegradability of polymer materials as evaluated by the modified Sturm test is labor-intensive, cumbersome and costly and also tends to cumulate errors. An automated system for the measurement of carbon dioxide would overcome many of these disadvantages. We describe here a method in which CO2 was determined by IR spectroscopy. We compared the results with those from trapping CO2 in a solution of barium hydroxide (Ba(OH)2) followed by manual titration. The automated system was more reproducible, less costly and more compact. The automated system could also be employed to measure the biodegradability of other substances such as oils and detergents.     

小麦生长周期中土壤Cu的迁移转化实验研究

通过盆栽试验,研究了不同土壤Cu添加浓度下,在小麦生长不同时期,小麦根区土壤与非根区土壤中总量Cu和有效态Cu的浓度,以此揭示其迁移转化特征。研究发现:小麦生长可以对土壤中的Cu进行吸收,拔节期小麦吸收能力最强;Cu添加有利于小麦对土壤中Cu的吸收,在试验水平下,添加浓度越高促进作用越明显,在200 mg/kg Cu添加浓度下,成熟期土壤中Cu含量较幼苗期减少了79%;小麦生长使土壤中有效态Cu占总量Cu的比重增加,并且使非根区土壤中Cu向根区土壤迁移。     

Harmonisation of ready biodegradability tests

Seven ready biodegradability tests (AFNOR, OECD, ISO, RDA, MITI(I), Sturm, Closed Bottle Test) have been assessed, with particular consideration of those aspects which are, at least in part, responsible for the variability in results. Proposals for harmonising certain test conditions, together with recommendations for minimising the effect of nitrification, are made.     

4种脂肪酸浮选捕收剂的生物降解性能研究

在好氧的条件下,以活性污泥为接种体,使用改良斯特姆法测试脂肪酸浮选捕收剂(油酸钠、9-羟基硬脂酸钠、硬脂酸钠、蓖麻油酸钠)的生物降解性能,并与利用BOD5/COD进行的可生化评价方法进行比较。结果表明:(1)油酸钠、蓖麻油酸钠的BOD5/COD分别为0.54、0.63,属易生物降解物质;9-羟基硬脂酸钠、硬脂酸钠的BOD5/COD分别为0.36、0.37,属可生物降解物质。(2)油酸钠、9-羟基硬脂酸钠、蓖麻油酸钠28d的生物降解率分别为88.6%、62.2%、100.0%,达到了经济合作与发展组织的OECD-301B生物降解性能实验标准,属于易生物降解物质;硬脂酸钠28d的生物降解率为49.8%,没有达到OECD-301B生物降解性能实验标准,属难生物降解物质。4种脂肪酸浮选捕收剂的生物降解性能依次为:蓖麻油酸钠油酸钠9-羟基硬脂酸钠硬脂酸钠。(3)当有机酸中存在碳碳双键和羟基时,有机酸的生物降解性能都会提高,并且碳碳双键的影响要大于羟基的影响;当二者同时存在时,生物降解性能会大幅度提高。     

Avoidance test with Enchytraeus albidus (Enchytraeidae): effects of different exposure time and soil properties

Enchytraeids are ecologically relevant soil species and are commonly used in standardized toxicity tests. Their rapid reaction to a chemical exposure can be used as a toxicological measurement endpoint that assesses the avoidance behavior. The objectives of this investigation were to determine the effects of soil properties on the avoidance behavior of Enchytraeus albidus and to optimize the duration of avoidance test. The avoidance tests included (1) exposures in OECD artificial soil with standard or modified properties (pH, clay or peat content), and (2) exposures to copper chloride, cadmium chloride, and to the organic pesticides dimethoate and phenmedipham for different time periods. Results showed that alteration of OECD soil constituents significantly affected the avoidance behavior of enchytraeids, and that the 48-h exposure was the optimal duration of the test. Consideration of soil properties is important for selecting appropriate experimental design and interpreting the results of the enchytraeid avoidance test.     

Characteristics of heavy metals in soils and grains of wheat and maize from farmland irrigated with sewage

The farmland irrigation with the sewage is a common and better pathway to save the resource of groundwater in Northern China. The investigation was conducted in the farmland along the Fuhe River to explore characteristics of heavy metals in soils and grains of wheat and maize from a long-term sewage-irrigated area of Baoding region. The results showed that the topsoil with long-term sewage irrigation accumulated more Cd, Pb, and Hg compared with that of soil irrigated with groundwater and their corresponding natural background values. Cd concentrations in 48% of sewage-irrigated soil samples exceeded the Chinese safety limitation at 0.6 mg/kg, but less Cd accumulated in crop grains and did not pose the potential health risk. On the contrary, Pb levels in soils irrigated with sewage were lower than the safety limitation but Pb concentrations in 24% of wheat grain samples exceeded the Chinese national safety limit. Long-term sewage irrigation did not increase As, Cr, and Ni concentrations in soils or crop grains. The target hazard quotient (THQ) of heavy metals in edible grains of crops was selected to assess their risk to human health. Total THQ values were higher than 1.0 for the wheat samples from sewage-irrigated area and both sewage-irrigated and smelter-impacted areas, and As is the main contributor to the total THQ and posed the potential risk to human health. Therefore, the accumulation of Cd, Pb, Hg, and As in soils and crops in sewage-irrigated area should be monitored continuously to ensure food safety and security.

     

Measuring the biodegradability of nonylphenol ether carboxylates, octylphenol ether carboxylates, and nonylphenol

We examined the biodegradability of several metabolites of C8- and C9-alkylphenol ethoxylates, including nonylphenoxyacetic acid (NPEC1), nonylphenoxyethoxyacetic acid (NPEC2), octylphenoxyacetic acid (OPEC1), octylphenoxyethoxyacetic acid (OPEC2), and nonylphenol (NP). Using OECD method 301B (modified Sturm method), OPEC1 and OPEC2 are readily biodegradable: both compounds exceeded 60% of theoretical CO2 formation (ThCO2) by day 28, and required less than 10 days to go from 10% to 60% ThCO2. Also using method 301B, NPEC1 and NPEC2 exceeded 60% ThCO2 at day 28, but did not meet the 10 day window. Using OECD method 301F, the manometric respirometry method that measures oxygen consumption, approximately 62% of NP was biodegraded in 28 days, but required more than 10 days to go from 10% to 60% biodegradation. While the validity of the "10-day window" is currently being debated within OECD, the data show that the common metabolites of C8- and C9-APEs are rapidly degraded in the test systems used, which strongly suggests that they would not accumulate or persist in the environment.     

Biodegradation of endosulfan by Mortieralla sp. strain W8 in soil: Influence of different substrates on biodegradation

To examine the bioremediation potential of Mortierella sp. strain W8 in endosulfan contaminated soil, the fungus was inoculated into sterilized and unsterilized soil spiked with endosulfan. Wheat bran and cane molasses were used as substrates to understand the influence of different organic materials on the degradation of endosulfan in soil. Strain W8 degraded α- and β-endosulfan in both sterilized and unsterilized soil. In unsterilized soil with wheat bran+W8, α- and β- endosulfan were degraded by approximately 80% and 50%, respectively after 28 d incubation against the initial endosulfan concentration (3 mg kg(-1) dw). The corresponding values for α- and β-endosulfan degradation with wheat bran only were 50% and 3%. Endosulfan diol metabolite was detected after 14 d incubation in wheat bran+W8 whereas it was not found with wheat bran only. Production of endosulfan sulfate, the main metabolite of endosulfan, was suppressed with wheat bran+W8 treatment compared with wheat bran only. It was demonstrated that wheat bran is a more suitable substrate for strain W8 than cane molasses. Wheat bran+W8 is a superior fungus and substrate mix for bioremediation in soil contaminated with endosulfan.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 micro g g(-1). The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4-6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

The influences of fly ash on stabilization for Cd in contaminated soils

Soil contaminated with potentially toxic metals (PTMs) has being a global environmental issue, which needs to be addressed on the priority basis. Fly ash (FA) is a kind of low-cost alkaline materials, which has been widely used in remediation of soil contaminated by PTMs, while the effects of FA on the stability for PTMs in contaminated farmland soil are still not clearly evaluated. In this study, cadmium (Cd) contaminated soil samples, collected from Shaanxi (SX), Hubei (HB), and Zhejiang (ZJ) province of China, were amended with FA addition (0, 1%, 2.5%, 5%, and 10% dose), and 1-year changes of Cd availability in soil samples were focused on. In addition, biological assessment method through pot culture was carried out to evaluate the reuse potential of Cd contaminated soils amended by FA. The result indicated that FA had a notable impact on decreasing the Cd mobility of SX soil (sand type), with 18.2~52.1% reduction in the DTPA extractable solution, followed by HB soil with 5.9~16.7% reduction, but no obvious effect of FA on ZJ soil (clay type) was observed. Furthermore, the results of pot experiment revealed that FA application could increase the biomass of Chinese cabbage. However, the DTPA extractable Cd in soils after planation and the Cd accumulation of plant increased. The results revealed that FA was not a promising soil stabilizer to immobilize HMs in Cd contaminated soil, and careful consideration should be given to Cd contaminated soils with FA restoration especially in their using for farmland productive due to the remaining risk of Cd bioavailability. These results also contributed to provide references for similar soil pollution remediation.

     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 μ g g^{? 1}. The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4–6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Application of different single extraction procedures for assessing the bioavailability of heavy metal(loid)s in soils from overlapped areas of farmland and coal resources

Heavy metal(loid) extraction from soils in overlapped areas of farmland and coal resources (OAFCR) is crucial in understanding heavy metal bioavailability in soil and the subsequent risks to crops and consumers. However, limited attention has been paid to the extraction procedure of heavy metal(loid)s in OAFCR soils in the research. This study therefore explored different single and mixed extraction procedures, such as acetic acid (HOAc), citric acid, ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA), ethylene diamine tetraacetic acid + ammonium acetate (EDTA+NH₄OAc), and total digestion (HNO₃-HClO₄-HF) to determine the bioavailability of As, Cd, Cr, Cu, Pb, and Zn in OAFCR soil in Xuzhou, China. The results showed the metal(loid) extraction capacity from soil of the different procedures could be ranked as AB-DTPA > EDTA+NH₄OAc > HOA_C > citric acid. The transfer ability of heavy metal(loid)s from soil to wheat tissues and from wheat roots to aerial parts was analyzed by calculating the bioconcentration factor and transfer factor, respectively. Transfer factors of all metal(loid)s were < 1 except Cr whose transfer factor from root to shell and straw were > 1. It is suspected that foliar uptake plays a dominant role in Cr uptake. Correlation analysis between the bioavailability of heavy metal(loid)s in soil and uptake in respective wheat tissues was performed to recommend the best extraction procedures for different studies. The results show that AB-DTPA extraction is recommended for Cu uptake to wheat roots, straws, shells and grains, Zn uptake to roots, and Cd uptake to roots and straws.

     

Algal tests with soil suspensions and elutriates: a comparative evaluation for PAH-contaminated soils

An algal growth inhibition test procedure with soil suspensions is proposed and evaluated for PAH-contaminated soil. The growth rate reduction of the standard freshwater green alga Pseudokirchneriella subcapitata (formerly known as Selenastrum capricornutum) was used as the toxicity endpoint, and was quantified by measuring the fluorescence of solvent-extracted algal pigments. No growth rate reduction was detected for soil contents up to 20 g/l testing five non-contaminated Danish soils. Comparative testing with PAH-contaminated soil elutriates and soil suspensions showed that the suspensions had toxicity endpoints 2.5-3000 times lower than tests with the corresponding elutriates. Algal growth inhibition tests with soil suspensions are recommended for screening purposes as a supplement to elutriate testing. Experiments with a phenanthrene-spiked soil, showed that the sorbed compound did not contribute to the toxicity. However, the soil did act as a reservoir for phenanthrene, allowing desorption to occur continuously during the algal test which maintained higher concentrations of phenanthrene in the dissolved phase. Phenanthrene-spiked soil incubated for 90 days before algal testing, resulted in a reduction of the toxicity to P. subcapitata by a factor of 76 (from EC10 = 0.3 to 23.6 g soil/l). However, during this 90-day period the total concentration of phenanthrene in the soil decreased by 38% (from 322 to 199 mg/kg) indicating that phenanthrene in the aged soil had become less bioavailable.     

Avoidance response of Enchytraeus albidus in relation to carbendazim ageing

In this study, avoidance response of Enchytraeus albidus to LUFA 2.2 soil contaminated with pesticide carbendazim was investigated. The aim was to clarify minimal test duration and temporal changes in avoidance response due to contamination ageing. Firstly, the concentration causing 50% avoidance (EC₅₀) was determined as 7.6 mg/kg. Then, test duration needed to reach this value (ET₅₀ = approximately 18 h) was identified. Finally, the capability of E. albidus avoidance test to reflect the changes of pollutant bioavailability was tested. The soil was spiked with carbendazim at the EC₅₀ concentration 1, 14, or 28 days before the test started and avoidance effects of fresh versus aged contamination were compared. The results indicated that enchytraeids preferred soil contaminated for 28 days prior to assay where carbendazim was probably less bioavailable than in freshly spiked soil. Our results open an interesting research area of potential use of avoidance tests for contaminant bioavailability assessment.     

Persistence of herbicide fenoxaprop ethyl and its acid metabolite in soil and wheat crop under Indian tropical conditions

The persistence of fenoxaprop ethyl {Ethyl (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionate} herbicide and its active metabolite fenoxaprop acid was investigated in soil and wheat crop. Fenoxaprop acid was prepared by alkaline hydrolysis of fenoxaprop ethyl. A HPLC method was developed in which fenoxaprop ethyl herbicide and its acid metabolite showed sharp single peak at 6.44 and 2.61 min respectively. The sensitivity of the method for ester and acid was 2 and 1 ng respectively with limit of detection of 0.1 and 0.05 μg mL^?1. The recovery of fenoxaprop ethyl and fenoxaprop acid from soil, wheat straw and grain ranged between 73.8–80.2%. In a field experiment fenoxaprop ethyl (Puma super® 10 EC) when applied to wheat crop at the rate of 120 g and 240 g a.i. ha^-1 as post emergence spray, fenoxaprop ethyl converted to fenoxaprop acid. Residues of fenoxaprop ethyl and acid dissipated in soil with a half-life of 0.5 and 7.3 days, respectively. At harvest no detectable residues of fenoxaprop ethyl or acid were observed in soil, wheat grain and straw samples.     

The influence of time on lead toxicity and bioaccumulation determined by the OECD earthworm toxicity test

Internationally agreed standard protocols for assessing chemical toxicity of contaminants in soil to worms assume that the test soil does not need to equilibrate with the chemical to be tested prior to the addition of the test organisms and that the chemical will exert any toxic effect upon the test organism within 28 days. Three experiments were carried out to investigate these assumptions. The first experiment was a standard toxicity test where lead nitrate was added to a soil in solution to give a range of concentrations. The mortality of the worms and the concentration of lead in the survivors were determined. The LC50s for 14 and 28 days were 5311 and 5395 microgPb g(-1)soil respectively. The second experiment was a timed lead accumulation study with worms cultivated in soil containing either 3000 or 5000 microgPb g(-1)soil. The concentration of lead in the worms was determined at various sampling times. Uptake at both concentrations was linear with time. Worms in the 5000 microg g(-1) soil accumulated lead at a faster rate (3.16 microg Pb g(-1)tissue day(-1)) than those in the 3000 microg g(-1) soil (2.21 microg Pb g(-1)tissue day(-1)). The third experiment was a timed experiment with worms cultivated in soil containing 7000 microgPb g(-1)soil. Soil and lead nitrate solution were mixed and stored at 20 degrees C. Worms were added at various times over a 35-day period. The time to death increased from 23 h, when worms were added directly after the lead was added to the soil, to 67 h when worms were added after the soil had equilibrated with the lead for 35 days. In artificially Pb-amended soils the worms accumulate Pb over the duration of their exposure to the Pb. Thus time limited toxicity tests may be terminated before worm body load has reached a toxic level. This could result in under-estimates of the toxicity of Pb to worms. As the equilibration time of artificially amended Pb-bearing soils increases the bioavailability of Pb decreases. Thus addition of worms shortly after addition of Pb to soils may result in the over-estimate of Pb toxicity to worms. The current OECD acute worm toxicity test fails to take these two phenomena into account thereby reducing the environmental relevance of the contaminant toxicities it is used to calculate.     

Effects of six selected antibiotics on plant growth and soil microbial and enzymatic activities

The potential impact of six antibiotics (chlortetracycline, tetracycline and tylosin; sulfamethoxazole, sulfamethazine and trimethoprim) on plant growth and soil quality was studied by using seed germination test on filter paper and plant growth test in soil, soil respiration and phosphatase activity tests. The phytotoxic effects varied between the antibiotics and between plant species (sweet oat, rice and cucumber). Rice was most sensitive to sulfamethoxazole with the EC10 value of 0.1 mg/L. The antibiotics tested inhibited soil phosphatase activity during the 22 days' incubation. Significant effects on soil respiration were found for the two sulfonamides (sulfamethoxazole and sulfamethazine) and trimethoprim, whereas little effects were observed for the two tetracyclines and tylosin. The effective concentrations (EC10 values) for soil respiration in the first 2 days were 7 mg/kg for sulfamethoxazole, 13 mg/kg for sulfamethazine and 20 mg/kg for trimethoprim. Antibiotic residues in manure and soils may affect soil microbial and enzyme activities.     

Predictive statistical modelling of cadmium content in durum wheat grain based on soil parameters

Regulatory limits on cadmium (Cd) content in food products are tending to become stricter, especially in cereals, which are a major contributor to dietary intake of Cd by humans. This is of particular importance for durum wheat, which accumulates more Cd than bread wheat. The contamination of durum wheat grain by Cd depends not only on the genotype but also to a large extent on soil Cd availability. Assessing the phytoavailability of Cd for durum wheat is thus crucial, and appropriate methods are required. For this purpose, we propose a statistical model to predict Cd accumulation in durum wheat grain based on soil geochemical properties related to Cd availability in French agricultural soils with low Cd contents and neutral to alkaline pH (soils commonly used to grow durum wheat). The best model is based on the concentration of total Cd in the soil solution, the pH of a soil CaCl₂ extract, the cation exchange capacity (CEC), and the content of manganese oxides (Tamm’s extraction) in the soil. The model variables suggest a major influence of cadmium buffering power of the soil and of Cd speciation in solution. The model successfully explains 88% of Cd variability in grains with, generally, below 0.02 mg Cd kg^?1 prediction error in wheat grain. Monte Carlo cross-validation indicated that model accuracy will suffice for the European Community project to reduce the regulatory limit from 0.2 to 0.15 mg Cd kg^?1 grain, but not for the intermediate step at 0.175 mg Cd kg^?1. The model will help farmers assess the risk that the Cd content of their durum wheat grain will exceed regulatory limits, and help food safety authorities test different regulatory thresholds to find a trade-off between food safety and the negative impact a too strict regulation could have on farmers.