Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.     

Octachlorinated dioxin in pulps and effluents: Where does it come from?

Studies on the formation/destruction of dioxins associated with the pulping of wood artificially impregnated with an industrial grade of pentachlorophenol lend support to an earlier observation that ambient dioxins deposition may not necessarily be a unique source of the higher chlorinated dioxins occasionally found in pulps and final effluent discharges. These dioxins, which seemingly occur in products from a wide range of pulping technologies including recycle operations, may also originate from pentachlorophenol-based fungicides.     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) from a refinery process for zinc oxide used in feed additives: a source of dioxin contamination in Chilean pork

The Republic of Korea found dioxin at concentrations exceeding the Korean maximum residue limit (MRL) in pork (2 pg TEQ g⁻¹ fat) imported from Chile in June 2008. Korea and Chile collaborated and investigated to find out the sources of contamination. An isotope dilution method and high resolution gas chromatography/mass spectrometry (HR-GC/MS) were used for the analysis of PCDD/Fs. PCDD/Fs were found from 2.17 to 36.7 pg TEQ g⁻¹ fat from Chilean pork. 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF were found as the major congeners in pork samples. 2,3,4,7,8-PeCDF showed the highest concentration and contributed about 30% among the congeners in most of the samples. 2,3,7,8-TCDD, 1,2,3,7,8,9-HxCDD, OCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 1,2,3,7,8,9-HxCDF, and OCDF were not detected or exist at background levels in the less contaminated samples. Remarkably high concentrations of PCDD/Fs were found in samples of zinc oxide (17 147 pg TEQ g⁻¹), zinc oxide based premix (6673 pg TEQ g⁻¹), and the residue crust (800 pg TEQ g⁻¹) in a mixing chamber in the feed mill. From the results of various investigations, this case concluded that zinc oxide in the feed was the major source of the dioxin contamination in pork. The dioxins were formed from a metal refinery process to collect zinc oxide.     

分点进水对倒置A2/O工艺脱氮除磷效果的影响

在传统A2/O工艺基础上,提出了将缺氧池置于厌氧池前面的分点进水倒置A2/O工艺。通过改变α（进入厌氧区的污水分量）与β（进入缺氧区的污水分量）的比例,考察对倒置A2/O工艺脱氮除磷效果的影响。实验结果表明,当α：β为7∶3时,达到最佳的脱氮除磷效率,分别为74.3%和71.2%。     

Effects of dioxins and polychlorinated biphenyls (PCBs) on thyroid function in infants born in Japan – the second report from research on environmental health

Dioxins (PCDD + PCDF) and polychlorinated biphenyl (PCB) are potentially hazardous compounds and have structural similarity to thyroid hormones. Our research group on “Dioxins and PCB in Human Milk” was organized in 1997 and has been active for the past three years. We collected breast milk from 80 mothers living in Tokyo, Saitama, Ishikawa and Osaka Prefecture in Japan at 5, 30, 150, 300 postpartum days and measured PCDDs, PCDFs and PCBs during 1998–1999. We added another 20 prefectures and cities during 1999–2000. Breast milk was obtained from 415 mothers at 30 postpartum days (breast-feeding group). Blood was taken from infants who were breast-fed at the age of 1 year for evaluation of thyroid and immune functions. Blood was also taken from 53 infants who were bottle-fed (bottle-feeding group) as a control. Serum T4, T3, FT4 and TSH levels in the breast-feeding (n=337) and bottle-feeding (n=53) groups were within normal ranges and were not significantly different between the two groups. Although there were a large geographic differences of dioxins and co-PCB content in breast milk, there were no differences in serum T4, T3, FT4, TSH levels and no significant correlation between the mean serum levels of TSH and TEQ in breast milk. There was a significant correlation between serum TSH at 1 year of age and that from blood on dried filter paper TSH at 5 days of age. We concluded that dioxin intake from breast milk in Japanese infants did not impair thyroid function. However, long-term effects remain to be evaluated.     

A case study of dioxin monitoring in and around an industrial waste incinerator in Korea

Many studies have been conducted that monitor and trace the sources of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) by comparing congener patterns of environmental samples with those of possible sources. In this study, we measured PCDD/F concentrations and compared congener patterns of samples of various media found in and around an industrial waste incinerator in Korea, including stack gas, fly ash, bottom ash, ambient air, soil, pine needle, and human blood. We obtained reliable data on the relationship between the PCDD/F distributions in these sources and the environment, and thus found indicators with which to assess the impact of such sources on the surrounding environment. In addition, the difference between the levels of PCDD/Fs in the blood of short-term workers and long-term workers demonstrates that these workers are exposed to the compounds produced by the indicator.     

Comprehensive study on parameter sensitivity for flow and nutrient modeling in the Hydrological Simulation Program Fortran model

Numerous parameters are used to construct the HSPF (Hydrological Simulation Program Fortran) model, which results in significant difficulty in calibrating the model. Parameter sensitivity analysis is an efficient method to identify important model parameters. Through this method, a model’s calibration process can be simplified on the basis of understanding the model’s structure. This study investigated the sensitivity of the flow and nutrient parameters of HSPF using the DSA (differential sensitivity analysis) method in the Xitiaoxi watershed, China. The results showed that flow was mostly affected by parameters related to groundwater and evapotranspiration, including DEEPFR (fraction of groundwater inflow to deep recharge), LZETP (lower-zone evapotranspiration parameter), and AGWRC (base groundwater recession), and most of the sensitive parameters had negative and nonlinear effects on flow. Additionally, nutrient components were commonly affected by parameters from land processes, including MON-SQOLIM (monthly values limiting storage of water quality in overland flow), MON-ACCUM (monthly values of accumulation), MON-IFLW-CONC (monthly concentration of water quality in interflow), and MON-GRND-CONC (monthly concentration of water quality in active groundwater). Besides, parameters from river systems, KATM20 (unit oxidation rate of total ammonia at 20 °C) had a negative and almost linear effect on ammonia concentration and MALGR (maximal unit algal growth rate for phytoplankton) had a negative and nonlinear effect on ammonia and orthophosphate concentrations. After calibrating these sensitive parameters, our model performed well for simulating flow and nutrient outputs, with R ² and E_NS (Nash–Sutcliffe efficiency) both greater than 0.75 for flow and greater than 0.5 for nutrient components. This study is expected to serve as a valuable complement to the documentation of the HSPF model to help users identify key parameters and provide a reference for performing sensitivity analyses on other models.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Effect of additives in the Neem formulations on deposition,volatilization and persistence of Azadirachtin in spruce foliage

Abstract

Foliar deposits, volatilization and persistence of azadirachtin‐A (AZ‐A) were investigated after application of four spray mixes prepared from a wettable powder (WP) and three emulsifiable concentrate (EC) formulations of neem. They were applied at the dosage rate of 50 g AI in 4 L/ha onto potted spruce seedlings in a laboratory spray chamber. Droplet‐size spectra and deposits were assessed using Kromekote^® card/glass plate collection units. Foliar residues [dislodgeable residues (DR), penetrated residues (PR) and total residues (TR)] of AZ‐A and their volatilization were measured by HPLC at different intervals of time up to 60 h after treatment. Differences in the droplet‐size spectra and deposit levels were observed among the four spray mixes due to the influence of additives present in them. Dissipation half‐lives (DT₅₀) of the DR, PR and TR in the foliage were low (range, 19.5 to 38.9 h) and varied according to the residue type and the spray mix used. The DT₅₀ values of the DR were consistently lower (range, 19.5 to 31.9 h) than those of the PR (range, 30.5 to 38.9 h) due to preferential loss of the surface residues. The low DT₅₀ values observed for the DR and TR in the foliage sprayed with the WP spray mix were attributed to the particulate nature of the deposit. AZ‐A volatilized appreciably from the DR rather than from the PR. The variations found in the amounts of AZ‐A volatilized (42 to 58%) and unaccountable (38 to 46%) from the initial TR values in spruce foliage, after 60 h, were attributed to the physical form of the deposits on the target surface and the influences of additives present in the different spray mixes.     

The impact of heavy metal pollution gradients in sediments on benthic macrofauna at population and community levels

The effect of sediment pollution on benthos was investigated in the vicinity of a large sewage treatment outflow at Incheon North Harbor, Korea. Animal size, vertical distribution and standard community parameters were analyzed along a 3 km transect line (n = 7). Univariate parameters showed a general trend of increasing species diversity with increasing distance from the pollution source. Multi-dimensional scaling analysis led to the clear separation of 3 locational groups, supporting gradient-dependent faunal composition. The innermost location was dominated by small sub-surface dwellers while the outer locations by large mid to deep burrowers. Looking for the size-frequency distribution, most abundance species (Heteromastus filiformis) showed the presence of larger size animals with increasing proximity to the pollution source. Meanwhile, species-specific vertical distributions, regardless of the pollution gradient, indicated that such shifts were due to species replacement resulting from a higher tolerance to pollutants over some species.     

蔬菜中有机磷农药残留研究及对策

以西安市为例,研究了蔬菜中有机磷农药的残留问题,分析了不同农药在蔬菜中的残留特征以及不同品种蔬菜、不同类型蔬菜中农药残留的特征,讨论了蔬菜中农药残留量超标的原因及相关对策。     

1H-NMR-based metabolomic study on toxicity of methomyl and methidathion in fish

A ¹H-nuclear magnetic resonance (NMR) spectroscopy with multivariate analysis was applied to detect the toxicity of antiacetylcholinesterase insecticides, methomyl (methyl (1E)-N-(methylcarbamoyloxy)ethanimidothioate) and methidathion (3-(dimethoxyphosphinothioyl sulfanylmethyl)-5-methoxy-1,3,4-thiadiazol-2-one), using zebrafish (Danio rerio) and Chinese bleak (Aphyocypris chinensis). Generally, methomyl and methidathion have been believed not to highly accumulate in fish tissues. However, these pesticides showed their toxicity by altering patterns of whole-body metabolites in neurotransmitter balance, energy metabolism, oxidative stress, and muscle maintenance in low concentrations. We used Pearson correlation analysis to contextualize the metabolic markers in pesticide treated groups. We observed that the positive correlations of choline with acetate and betaine in untreated control were shifted to null correlations showing acetylcholinesterase specific toxicity. This research demonstrated the applicability and potential of NMR metabolomics in detecting toxic effects of insecticide with a modicum of concentrations in aquatic environment.     

鸭河口水库水体总氮、总磷预测研究

根据鸭河口水库受纳点源及面源污染负荷情况,选择枯水期为预测时期,采用迪隆模型对鸭河口水库水体总氮、总磷进行预测研究,为鸭河口水库水质保持和富营养化防治提供基础数据。     

Toxic effects of chlorpyrifos on lysozyme activities,the contents of complement C3 and IgM,and IgM and complement C3 expressions in common carp (Cyprinus carpio L.)

Chlorpyrifos is one of the organophosphate pesticides widely used in agricultural practices throughout world. It has resulted in a series of toxicological and environmental problems, such as impacts on many non-target aquatic species, including fish. In the present study, toxic effects of chlorpyrifos on lysozyme activities, contents of IgM and complement C3, and the expressions of IgM and complement C3 at mRNA level in common carp were evaluated by acute exposure of 15 (1/10 LC₅₀) or 75 μg L⁻¹ (1/2 LC₅₀) of chlorpyrifos for 7 d. The results of acute toxicity tests showed that the 96 h-LC₅₀ of chlorpyrifos for common carp was determined to be 149 μg L⁻¹. We also found that chlorpyrifos promoted lysozyme activities at the earlier stages of exposure but inhibited it at the late stages in the serum, hepatopancreas, and spleen of common carp. Furthermore, it was observed that chlorpyrifos-exposure decreased IgM contents in fish serum and spleen while increased it in kidney. No obvious change was found in the contents of complement C3 in fish spleen, while a slight increase of complement C3 was observed in fish serum and kidney after 1 d of chlorpyrifos-exposure. In addition, the results of quantitative real-time PCR showed that IgM and complement C3 expressions were up-regulated at the earlier stage of exposure but down-regulated at later stage. Our results indicate that chlorpyrifos causes immunotoxicity to common carp.     

Inferring chemical effects on carbon flows in aquatic food webs: Methodology and case study

The majority of ecotoxicological enclosure experiments monitor species abundances at different chemical concentrations. Here, we present a new modelling approach that estimates changes in food web flows from such data and show that population- and food web level effects are revealed that are not apparent from abundance data alone. For the case of cypermethrin in freshwater enclosures, photosynthesis and excretion (d⁻¹) of phytoplankton at 3.643 μg L⁻¹ cypermethrin were 30% lower and 100% higher than in the control, respectively. The ingestion rate of mesozooplankton (d⁻¹) was 6 times higher in the treated enclosures than in the control as food concentration increased with insecticide exposure. With increasing cypermethrin concentrations, nanoflagellates progressively relied on phytoplankton as their main food source, which rendered the food web less stable. We conclude that this tool has excellent potential to analyse the wealth of enclosure data as it only needs species abundance and general constraints.     

The association between maternal nonylphenol exposure and parity on neonatal birth weight: A cohort study in Taiwan

Background

The aim of this study was to explore the association between NP exposure and parity and their effect on neonatal birth weight.

Methods

A cohort of pregnant women was established in a medical center in North Taiwan. Urinary NP concentration was determined by high-performance liquid chromatography coupled with fluorescent detection and adjusted using creatinine. A multivariable regression model was fit to determine the association between the maternal NP level in each trimester and neonatal birth weight. The odds ratios (ORs) of infant birth weight below the 10th, 25th, and 50th percentiles, comparing pregnant women with the different NP exposure levels, was estimated using a logistic regression.

Results

Of the 162 pregnant women in the study, 99 were multiparas and 63 were primiparas. After adjusting for other covariates, the NP level in the second trimester had a significant association with birth weight in the primiparas (β = −182.49 g, p value = 0.02). The OR of low infant birth weight, comparing pregnant women with different NP levels, was increased by decreasing the cutoff percentile for birth weight (OR = 1.18 for the 50th percentile, 2.12 for the 25th percentile, and 7.81 for the 10th percentile). The odds of primiparas with high NP level having a low neonatal birth weight increased to 3.87, 11.77, and 9.40 for the three different percentiles (p value < 0.05).

Conclusion

Maternal NP exposure level is associated with an increased risk of low neonatal weight. Primiparas are especially at risk, and the second trimester of pregnancy may be the critical stage of exposure.     

水解酸化-缺氧法处理采油废水的污染物迁移降解试验研究

水解酸化．缺氧法对采油废水有较好的处理效果，采用GC／MS技术对水解酸化-缺氧法处理采油废水过程中污染物的迁移降解进行的研究表明：水解酸化段和缺氧段对采油废水中碳原子为C6-C9、分子量为100—140的有机物均有较好的降解能力。其中，在水解酸化段中酮类、芳烃得到较好的降解，缺氧段中酚类和醚类化合物降解明显。水解酸化-缺氧工艺对于采油废水中的甲苯和二甲苯具有较好的降解能力。     

Effect of sewage amendment on the dissipation of terbuthylazine,its degradation compound desethyl-terbuthylazine,and S-metolachlor in a field study

This study evaluates the effect of sewage amendment (SA) on the dissipation of terbuthylazine, its degradation compound desethyl-terbuthylazine, and S-metolachlor in the soil. The experiment was conducted at Padua Experimental Farm (Italy). Herbicides dissipation was evaluated in soils differently fertilized for three years: with inorganic fertilizer, with sewage sludge, and with a combination of them. Terbuthylazine and S-metolachlor were applied on sorghum as a formulated product at a dose of 2.8?L ha^?1, and their dissipation was followed for 2.5 months. The concentrations of herbicides and one metabolite in soil were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine and S-metolachlor followed a pseudo first order kinetics; they dissipated faster in soil amended only with inorganic fertilizer than in soils amended with sewage or sewage?+?inorganic fertilizer. The reduction in mineralization of the herbicides after sewage addition can be attributed to the reduced herbicide availability to microorganisms. The degradation of terbuthylazine led to the formation of desethyl-terbuthylazine. SA slowed down the formation and the degradation of desethyl-terbuthylazine, leading to a higher amount measured at the end of the incubation. These findings have practical implications for the assessment of the environmental fate of terbuthylazine and S-metolachlor in agricultural areas.     

Laboratory study highlights the key influences of stormwater sediment thickness and bioturbation by tubificid worms on dynamics of nutrients and pollutants in stormwater retention systems

In urban area, the accumulation of polluted stormwater sediments (SWS) in retention ponds may be a source of dissolved pollutants and nutrients for the aquatic ecosystems. Our objective was to quantify the influence of the thickness of SWS layer and the occurrence of tubificid worms on organic matter processing (O(2) uptake and fluxes of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon between sediment and water), releases of 17 PAHs and 4 heavy metals, and microbial characteristics. Results showed that oxidation of SWS organic matter (O(2) and NO(3)(-) uptakes) and releases of nutrients were significantly increased by the quantity of accumulated SWS and the worm bioturbation. Releases of acenaphtene and naphthalene from sediments were significantly increased by the thickness of the SWS layer. In contrast, tubificid worms did not promote the mobilization of pollutants. In conclusion, biological activities and stormwater sediment characteristics need to be assessed to quantify the fate of pollutants and nutrients in stormwater retention ponds.