Determination of octanol-air partition coefficients and supercooled liquid vapor pressures of organochlorine pesticides

Octanol-air partition coefficients (K_OA) and supercooled liquid vapor pressures (P_L) of nine organochlorine pesticides (OCPs) including p,p′-DDE, p,p′-DDD, o,p′-DDT, o,p′-DDE, o,p′-DDD, α-HCH, β-HCH, γ-HCH, δ-HCH were determined as functions of temperature using a gas chromatographic retention time method. Among them, the K_OA of o,p′-DDE and o,p′-DDD and the P_L of o,p′-DDE, o,p′-DDD, β-HCH and δ-HCH were determined for the first time. The determined K_OA and P_L values of investigated compounds at 25°C ranged from 3.14 × 10⁷ (α-HCH) to 3.76×10⁹ (p,p′-DDD), and 8.95×10^{? 4} Pa (p,p′-DDD) to 1.08×10^{? 1} Pa (α-HCH), respectively. The K_OA and P_L data were compared with published data. The K_OA values of o,p′-DDT at 25°C were 3.23×10⁹, higher than o,p′-DDE (1.02×10⁹) and o,p′-DDD (2.01×10⁹), indicating o,p′-DDT were more preferred to partition in soil compared with the metabolites. The K_OA values were lower and P_L values were higher for o,p′-DDE and o,p′-DDD, compared with their p,p′-isomeric counterparts, leading to a potential difference in behavior and fate of these isomers. The discrepancies among chemicals are obvious, which reflected in the increasing K_OA and decreasing P_L values in order of α-HCH, γ-HCH, β-HCH, δ-HCH, o,p′-DDE, p,p′-DDE, o,p′-DDD, o,p′-DDT, p,p′-DDD. For each compound, the LogK_OA decreased linearly with reciprocal absolute temperature, while LogP_L had a significant positive correlation with the inverse absolute temperature. The present study suggested that the method of gas chromatographic retention time was appropriate to measure the K_OA and P_L of a number of OCPs.     

南水北调西线一期工程调水河流之间实施补偿调度的可能性分析

以道孚、绰斯甲、足木足水文站1960～2000年的同步天然年径流量系列为基础,应用Copula方法构造了南水北调西线一期工程调水河流之间的径流联合分布模型,具体分析了鲜水河、绰斯甲河、足木足河这3条调水河流之间实施补偿调度的概率。结果表明：鲜水河与足木足河之间实施补偿调度的可能性最大,绰斯甲河与足木足河之间实施补偿调度的可能性次之,鲜水河与绰斯甲河之间实施补偿调度的可能性最小,其概率分别为4374％、3884％和2582％。
     

Atmospheric organochlorine pesticide (OCP) levels in a metropolitan city in Turkey

Air concentrations of organochlorine pesticides (OCPs) were measured at four different sites in Bursa, Turkey to determine current levels. For this purpose, about 35 samples were collected from June 2008 to June 2009 using a high volume air sampler (HVAS) equipped with particle and gas-phase units. Ten OCP compounds (alpha-, beta-, gamma-, delta-hexachlorocyclohexane, Heptachlor epoxide, Endrin, Endosulfan beta, Endrin aldehyde, p,p′-DDT and Methoxychlor) were reported within the scope of this study. The average concentrations of total (particle + gas) ∑OCPs were 550.9 ± 277.6 pg m⁻³ (coastal), 1030.7 ± 453.5 pg m⁻³ (urban/traffic), 519.7 ± 277.5 pg m⁻³ (semi-rural) and 722.8 ± 351.8 pg m⁻³ (urban/residential). The individual OCP concentrations were in line with reported concentrations. The maximum particle and gas-phase concentrations were determined for Endosulfan beta and beta-HCH for all sites, respectively. Available gas/particle partitioning models were applied in order to investigate the compatibility of the experimental data and the significant relationships were observed.     

Atmospheric phenanthrene pollution modulates carbon allocation in red clover (Trifolium pratense L.)

The influence of atmospheric phenanthrene (PHE) exposure (160 μg m⁻³) during one month on carbon allocation in clover was investigated by integrative (plant growth analysis) and instantaneous ¹³CO₂ pulse-labelling approaches. PHE exposure diminished plant growth parameters (relative growth rate and net assimilation rate) and disturbed photosynthesis (carbon assimilation rate and chlorophyll content), leading to a 25% decrease in clover biomass. The root-shoot ratio was significantly enhanced (from 0.32 to 0.44). Photosynthates were identically allocated to leaves while less allocated to stems and roots. PHE exposure had a significant overall effect on the ¹³C partitioning among clover organs as more carbon was retained in leaves at the expense of roots and stems. The findings indicate that PHE decreases root exudation or transfer to symbionts and in leaves, retains carbon in a non-structural form diverting photosynthates away from growth and respiration (emergence of an additional C loss process).     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

On the origin of elevated levels of persistent chemicals in the environment

In general, contamination levels tend to be highest close to sources of a chemical and decline with increasing distance as a result of dilution, dispersion and degradation. However, contrary to this, circumstances have been described when contamination levels are higher further away from sources than at the sources themselves. Examples are elevated levels of persistent, hydrophobic, organic chemicals in the Arctic, in mountain regions and in forest soils. In order to address the questions of why and when such an inversion of environmental levels is occurring, this paper seeks to identify, name and categorise principles of general validity leading to such behaviour. By compiling and analysing various causes of elevated contamination levels in the environment, three main categories became apparent, 1. equilibrium partitioning effects, 2. effects resulting from changes in phase composition, volume or temperature, and 3. dynamic or kinetic effects. These principles are illustrated with several examples. The case can be made that understanding, quantifying and predicting these causes could provide a general conceptual framework for studying the fate of chemicals in the environment.     

区域沉积物质量基准常用建立方法的改进与优化

建立区域沉积物质量基准（SQC）具有重大的社会、经济和环境价值。本文选择两种当前流行的基准建立方法,相平衡分配法（EqP）和质量三合一法（Triad）,重点阐述在指标选择与定量、误差模拟校正、模式拟和运算等实施操作方面各自的改进与优化。同时探讨了SQC的发展趋势以及在污染沉积物治理与恢复决策中的作用。     

Cold comfort: Arctic seabirds find refugia from climate change and potential competition in marginal ice zones and fjords

Climate change alters species distributions by shifting their fundamental niche in space through time. Such effects may be exacerbated by increased inter-specific competition if climate alters species dominance where competitor ranges overlap. This study used census data, telemetry and stable isotopes to examine the population and foraging ecology of a pair of Arctic and temperate congeners across an extensive zone of sympatry in Iceland, where sea temperatures varied substantially. The abundance of Arctic Brünnich’s guillemot Uria lomvia declined with sea temperature. Accessibility of refugia in cold water currents or fjords helped support higher numbers and reduce rates of population decline. Competition with temperate Common guillemots Uria aalge did not affect abundance, but similarities in foraging ecology were sufficient to cause competition when resources are limiting. Continued warming is likely to lead to further declines of Brünnich’s guillemot, with implications for conservation status and ecosystem services.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01650-7.     

硫丹对草鱼Ⅰ相、Ⅱ相酶活性及DNA损伤的影响

研究了硫丹对草鱼肝脏Ⅰ相酶氨基比林-N-脱甲基酶（APND）和红霉素-N-脱甲基酶（ERND）、Ⅱ相酶谷胱甘肽-S-转移酶（GST）活性及DNA受损细胞彗星尾长（TL）和尾部DNA含量（%TDNA）的影响。试验共设置0.18、0.36和0.71μg.L-1 3个暴露浓度组和1个空白对照组,分别在试验24、72、120和168 h时取样测定各指标。结果表明,24 h时,0.36和0.71μg.L-1暴露组草鱼肝脏APND活性与对照组相比显著升高（P〈0.05或P〈0.01）,72 h时受到显著抑制（P〈0.01）;120 h后各暴露组APND活性与对照组相比均表现为受到显著抑制（P〈0.05或P〈0.01）。ERND活性总体表现为受诱导。GST活性总体呈先受诱导后受抑制的变化趋势;0.36和0.71μg.L-1暴露组GST活性均在72 h时达到最高值,之后随暴露时间的延长缓慢降低,并在168 h时表现为受抑制;0.18μg.L-1暴露组在120 h时达到最大值,之后降低,168 h时GST活性与对照组水平相当。经硫丹暴露后,草鱼肝脏细胞DNA明显受损,TL与%TDNA均随硫丹浓度的升高或暴露时间的延长而增加,且相关显著。硫丹可影响草鱼肝脏Ⅰ相、Ⅱ相代谢酶活性,并对肝细胞DNA造成遗传损伤。     

西安城区大气中多氯联苯的气粒分配研究

为了解西安城区大气中多氯联苯(PCBs)的气粒分配规律,于2012年春季对西安城区大气中气态和颗粒态样品进行每周一次的主动采样.结果表明,西安城区大气中PCBs的总浓度(气态和颗粒态)为62.05~454.18pg/m3,主要以气态为主.由Clausius-Clapeyron方程得到的斜率较陡(-5193.24),表明春季大气中的PCBs主要受西安城区附近地面挥发释放的影响.PCBs的气粒分配系数(KP)与过冷饱和蒸汽压(PoL)高度相关,由logKP和logPoL线性回归得到的斜率mr(-0.46~-0.37)均高于平衡状态理论值-1,说明西安城区大气中的PCBs气粒分配尚未达到平衡状态.采用Junge-Pankow吸附模型和Harner-Bidleman吸收模型对PCBs颗粒态百分比(φ)及KP进行了模拟,结果显示两种模型均较好地预测了PCBs的气粒分配行为,但与实验测得的值相比,两种模型均高估了φ值及KP值.