Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

Female choice in sage grouse: the roles of attraction and active comparison

Previous studies of female choice in sage grouse Centrocercus urophasianus have implicated both the acoustic quality and repetition rate of the stereotyped strut display as putative cues for female choice. Stages in the choice process at which specific components of male courtship display influence female decisions were investigated using field observations of female pre-mating behavior. Females visited a subset of territorial males and then actively chose one of these as a mate. The order in which males were visited suggested that females searched until an acceptable mate was found, rather than employing a “best-of-n” tactic. Numbers of females visiting a male were related to differences in an acoustical component of display (inter-pop interval) whereas the probability that a visiting female mated was related to display rate (Table 3), indicating that initial attraction and active choice are influenced by different components of display. In addition, inter-pop interval and display rate tended to covary inversely (Fig. 1), suggesting that attraction and active choice may impose conflicting selection pressures on display performance. Received: 11 November 1995/Accepted after revision: 16 March 1996     

Investigation of fault position and sources of radon by measurement of 238U decay series radionuclide activity in soil samples

North Derbyshire is designated a Radon Affected Area by the National Radiological Protection Board of Great Britain since more than 1% of the housing stock is estimated to have radon levels in excess of the 200 Bq m-3 Action Level. Enhanced radon emissions associated with geological faults make knowledge of their position important in relation to any potential residential or industrial development. A general survey of radionuclides present in the soils of north Derbyshire and their relationship to the underlying geology highlighted the difficulty of identifying the position of geological faults in the field. Using gamma-ray spectroscopy of soil samples the activity of three 238U decay series radionuclides (226Ra, 214Pb and 214Bi), which were taken as evidence of the presence of 222Rn which occurs in the same decay series, was measured to indicate the position of a fault by enhanced activity. The results also provided some evidence of the source of radon emitted at the fault. A comparison of this methodology with the more conventional soil gas analysis method is made.     

Assessment of future climate change impacts on water-heat-salt migration in unsaturated frozen soil using CoupModel

• A model coupling water-heat-salt of unsaturated frozen soil was established. • Future temperature, precipitation, and evaporation increase in freeze–thaw period. • Soil water, heat, and salt transport are closely coupled during freeze–thaw period. • Freeze–thaw cycles and future climate change can exacerbate salinization. The transport mechanisms of water, heat, and salt in unsaturated frozen soil, as well as its response to future climate change are in urgent need of study. In this study, western Jilin Province in north-eastern China was studied to produce a model of coupled water-heat-salt in unsaturated frozen soil using CoupModel. The water, heat, and salt dynamics of unsaturated frozen soil under three representative concentration pathway (RCP) scenarios were simulated to analyze the effects of future climate change on unsaturated frozen soil. The results show that water, heat, and salt migration are tightly coupled, and the soil salt concentration in the surface layer (10 cm) exhibits explosive growth after freezing and thawing. The future (2020–2099) meteorological factors in the study area were predicted using the Statistical Downscaling Model (SDSM). For RCP2.6, RCP4.5, and RCP8.5 scenarios, future temperatures during the freeze–thaw period increased by 2.68°C, 3.18°C, and 4.28°C, respectively; precipitation increased by 30.28 mm, 28.41 mm, and 32.17 mm, respectively; and evaporation increased by 93.57 mm, 106.95 mm, and 130.57 mm, respectively. Climate change will shorten the freeze–thaw period, advance the soil melting time from April to March, and enhance water and salt transport. Compared to the baseline period (1961–2005), future soil salt concentrations at 10 cm increased by 1547.54 mg/L, 1762.86 mg/L, and 1713.66 mg/L under RCP2.6, RCP4.5, and RCP8.5, respectively. The explosive salt accumulation is more obvious. Effective measures should be taken to prevent the salinization of unsaturated frozen soils and address climate change.     

Assessment of relative bioavailability of heavy metals in soil using in vivo mouse model and its implication for risk assessment compared with bioaccessibility using in vitro assay

There is limited study to simultaneously determine the relative bioavailability of heavy metals such as Cd, Pb, Cu, Cr(VI), and Ni in soil samples. In the present study, the bioaccessibility of heavy metals using in vitro assay was compared with the relative bioavailability of heavy metals using in vivo mouse model. The bioaccessibility of heavy metals ranged from 9.05 ± 0.97 % (Cr) to 42.8 ± 3.52 % (Cd). The uptake profile of heavy metals in soil and solution samples in mouse revealed that the uptake kinetics could be fitted to a two-compartment model. The relative bioavailability of heavy meals ranged from 34.8 ± 7.0 % (Ni) to 131 ± 20.3 % (Cu). Poor correlation between bioaccessibility and relative bioavailability of heavy metals was observed (r ² = 0.11, p > 0.05). The relative bioavailability of heavy metals was significantly higher than the bioaccessibility of heavy metals (p < 0.05). The present study indicated that the in vitro digestion method should be carefully employed in risk assessment.     

Assessment of As and Heavy Metal Contamination in the Vicinity of Duckum Au-Ag Mine, Korea

In order to assess the potential of As and heavy metal contamination derived from past mining activity and to estimate the human bioavailability quotients for As and heavy metals. Tailings, soils and crop samples were collected and analysed for As, Cd, Cu, Pb and Zn. The mean concentrations of As, Cd, Cu, Pb and Zn in the tailings were 68.5, 7.8, 99, 3,754 and 733 µg g^–1, respectively. Maximum Pb concentration in tailings was up to 90 times higher than its tolerable level. The concentrations of these metals were highest in the soils from the dressing plant area, and decreased in the order: farmland soil to paddy soil. In particular, some of the soils from the dressing plant area contained more than 1% of Pb and Zn. The pollution index ranged from 0.19 to 1.93 in paddy soils, and from 1.47 to 3.60 in farmland soils. The average concentrations of heavy metals in crops collected from farmland were higher than those in rice stalks or rice grains, and higher than the internationally accepted limits for vegetables. Element concentrations extracted from farmland soils within the simulated human stomach for 1 h are 9.4 mg kg^–1 As, 3.8 mg kg^–1 Cd, 37 mg kg^–1 Cu, 250 mg kg^–1 Pb and 301 mg kg^–1 Zn. In particular, the extracted concentrations of Cd, Pb and Zn are in excess of the tolerable levels. The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion (by inhalation and from dirty hands) of soils by the local population could pose a potential health threat due to long-term toxic element exposure.     

桂林市土壤和蔬菜镉含量调查及食用安全性评估

对桂林市蔬菜和菜地土壤镉含量进行调查,评价其累积状况,并评估人体经食用蔬菜摄入镉的安全性。结果显示,桂林市菜地土壤镉含量空间变异较大,呈现西北部和西南部低、东北部和东南部高的分布特点;与背景样点相比,菜地土壤镉累积效应显著,土壤镉含量范围、中值、算术均值和几何均值分别为0.056～17.35、0.624、1.193和0.696 mg.kg-1,超标率为85.5%。蔬菜镉含量范围、中值和几何均值分别为0.09～663.2、29.4和29.2μg.kg-1(以鲜质量计),综合超标率为4.95%;叶菜类蔬菜镉含量显著高于根茎类和瓜果类,花菜、韭菜、大白菜、大葱、芋头、豆苗、萝卜、菠菜、大蒜和蕃茄的镉富集系数较低,抗镉污染能力较强。桂林市居民人均通过食用蔬菜的镉摄入量为9.08μg.d-1,对普通人群不存在明显的食用安全风险。     

土壤中元素碳的测定与研究

采用化学方法测定土壤中元素碳的含量。取黄土样品做本方法的平行性实验,平行性良好。取不同粒度周口店土样做对比实验,粒径小于710 mm的原始样元素碳回收最高。同时对元素碳的来源、测定方法、研究意义进行了初步探讨。     

四种改良剂对Cu、Cd复合污染土壤中Cu、Cd形态和土壤酶活性的影响

以黑麦草（Lolium perenne L.）作为修复植物进行田间试验,研究了石灰、磷灰石、蒙脱石、凹凸棒石4种改良剂对铜镉复合污染土壤中Cu、Cd形态和土壤酶活性的影响。结果表明,改良剂提高了污染土壤pH,降低了土壤可交换态（EX）Cu、Cd含量;改良剂提高了土壤脲酶、酸性磷酸酶和过氧化氢酶活性,每种改良剂对土壤酶活性增加幅度随其添加剂量增加而增大;土壤酶活性与土壤EX态Cu、Cd含量呈显著或极显著负相关关系,与土壤pH呈显著或极显著正相关关系;高剂量石灰（石灰占污染土壤耕作层质量的0.4%）和高剂量磷灰石（磷灰石占污染土壤耕作层质量的2.32%）处理钝化污染土壤中Cu、Cd及提高土壤酶活性效果最好。     

Assessment of Groundwater Quality and Contamination from Uranium-Bearing Black Shale in Goesan–Boeun Areas, Korea

This study was initiated to identify the impact of metals and uranium enriched soil and black shale in groundwater quality and contamination. From a Piper diagram, groundwater was classified into four types as (Ca+Mg)–HCO₃ type, (Ca+Mg)–SO₄ type, the mixed type of these two and Na–HCO₃ type, reflecting the complicated nature of geology of the study area. Silicate weathering appeared to be the major water–rock interaction. In groundwater, metals including Cr, Pb, Cu and V, previously identified as being enriched in soils and black shale, were much lower in concentrations than Korean and US EPA drinking water guidelines. Instead, Fe and Mn caused major water-quality problems. In the artesian groundwater from an abandoned uranium mine, the uranium concentration was 21.3 µg L^–1, slightly higher than EPA guidelines of 20 µg L^–1. Heavy metals in groundwater appeared to be controlled mostly by sorptions on to Fe- and Mn-oxyhydroxides. They could be remobilised in groundwater with changes of pH and Eh conditions due to acid mine drainage from black shale or the recharge of fresh water. Uranium would be associated with carbonate and sulphate complexes in groundwater. Because of the remaining water-quality problems in the study area, we suggested containment of identified mine wastes, considering remedial measures for local problems with Fe and Mn, continuous monitoring of groundwater and developing groundwater from deep aquifers.     

羟基磷灰石对棕壤和红壤铜吸附的影响

采用等温平衡法,观测了羟基磷灰石对红壤、棕壤铜吸附量的影响,并应用Freundlich方程Cs=KfCen分析了土壤铜的吸附特征。结果表明,棕壤对铜的吸附能力明显高于红壤。以n（磷）∶n（铜）=1∶1向棕壤与红壤中施用羟基磷灰石,会增加两种土壤对铜的吸附量。其中,羟基磷灰石影响红壤对铜吸附能力明显高于棕壤。增加羟基磷灰石的施用量,会增加红壤与棕壤对铜的吸附量,提高土壤铜的吸附能力。高量羟基磷灰石[n（磷）∶n（铜）=4∶1]的作用效果最为明显;与对照相比,铜的吸附量分别增加62.1%和28.4%。据此推测,在铜污染红壤或棕壤上,可以选用羟基磷灰石作为磷肥的肥源。     

超高效液相色谱串联质谱法测定霜霉威在番茄和土壤中残留及消解动态

应用所建立的分散固相萃取-液相色谱-串联质谱法测定土壤和番茄中霜霉威为0.02、0.20、2.00 mg·kg-1等3个添加浓度时,日内平均回收率为83.9%—104.6%,日内相对标准偏差为1.0%—5.5%,日间平均回收率为84.3%—108.9%,日间相对标准偏差为1.4%—4.9%.霜霉威在1.0—200.0μg·L-1浓度范围内相关系数R20.9992,在土壤中和番茄基质中定量限均为0.02 mg·kg-1.该方法能够满足现有限量标准的要求.霜霉威消解动态试验采用推荐高剂量(90 g·ha-1)为施药剂量,在植株第2穗果膨大期开始喷药1次,分别测定喷药后2 h、1 d、2 d、4 d、7 d、14 d的霜霉威残留量的变化.浙江杭州、山东潍坊和河南商丘的3个试验点消解动态试验中,降解动态符合一级动力学指数模型.2011—2012年霜霉威在番茄中降解半衰期为2.4—4.7 d,在土壤中降解半衰期1.1—1.5 d.施药5 d后的残留量均小于检测限,远远低于2.0 mg·kg-1最大残留限量,实际样品中霜霉威的残留量均低于检测限.72.2%霜霉威水剂按照推荐剂量1.5倍喷施番茄1次,其喷施2 h后的残留量仅为1.5 mg·kg-1,符合残留要求可以安全使用.     

Phytotoxicity assessment of phenanthrene and pyrene in soil using two barley genotypes

This study investigated the toxicity extent of phenanthrene and pyrene to two cultivars (CM-72 and Gairdner) of barley (Hordeum vulgare). Germination of barley seeds was evaluated in 69-d aged soil, separately spiked with phenanthrene at extractable concentrations of 0.95, 6.3, 59, and 300 mg kg^?1 (dry soil) and pyrene at 1.0, 9.0, 73, and 400 mg kg^?1 (dry soil). Although germination was not inhibited, significant (P < 0.05) reduction in root and shoot length occurred at concentrations of phenanthrene ≥6.3 mg kg^?1 and pyrene ≥9.0 mg kg^?1 after both 72 and 240 h. Fresh and dry biomass of both cultivars reduced with increasing concentrations of both polycyclic aromatic hydrocarbons (PAHs). Barley cultivar CM-72 was more sensitive than Gairdner, and it can be considered suitable for toxicity assessment of PAH-contaminated soils.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

长期不同施肥对红壤Cu和Cd含量及活化率的影响

对始于1990年的红壤旱地施肥长期定位试验的6个处理包括对照(不施肥,CK)、施氮(N)、氮磷(NP)、氮磷钾(NPK)、氮磷钾+有机肥(NPKM)和有机肥(M)的历年耕层土壤重金属Cu和Cd全量和有效态含量进行分析,以阐睨长期不同施肥条件下红壤Cu、Cd含量及活化率变化特征.结果表明,16 a连续不施肥或施用化肥(N/NP/NPK)条件下土壤Cu、Cd全量和有效态含量基本保持不变;Cu活化率随施肥时间变化不显著,但Cd的活化率在施肥后期(1996-2006)呈明显上升趋势,在施氮处理上高达95.7%;不施肥和配施化肥下Cd的活化率与土壤pH值呈极显著负相关.化肥配施有机肥(NPKM)和单施有机肥处理(M)的土壤中Cu、Cd全量和有效态含量及其活化率随时间均呈显著上升趋势;土壤Cd含量从1990年的0.12 mg·kg-1 上升为2006年的1.31～1.48 mg·kg-1,平均年上升0.08～0.09 mg·kg-1;土壤有效态Cd含量2006年达到0.53～0.58 mg·kg-1,为1990年的18.0～19.9倍;Cd活化率与土壤有机质含量呈显著正相关.长期施用有机肥红壤Cu、Cd含量超标严重,土壤Cu和Cd全量之间达极显著相关(r=0.887**,n=30),其来源具有一致性,有机肥为环境带来的风险应予以重视.     

Efficacy of rapeseed residue and eggshell waste on enzyme activity and soil quality in rice paddy

Addition of plant residue into soils improves soil physiochemical properties and its fertility. Rapeseed residue is an emerging N source to paddy soils via rice-rape double-cropping practice. The objective of this study was to evaluate the effects of rapeseed residue and eggshell waste on chemical changes and enzyme activity in the rice paddy soil. The powdered eggshells at 0, 1, 3, and 5% were applied once to 7.0 kg paddy repacked soils in each pot treated with the rapeseed residue or the conventional N, P, and K fertilisers. Eight rice seedlings (Oriza sativa L. cv. Ilmibyeo) (40 days after sowing) were transplanted to the treated each pot. The contents of total C (TC) and N (TN), and organic matter (OM) were significantly increased in soils treated with the rapeseed residue compared to the N, P, and K fertilisers. With the addition of eggshell containing ～92% CaCO₃, a considerable increase of soil pH was observed in soils treated with the rapeseed residue and the N, P, and K fertilisers, compared to the untreated soil. Activities of β-glucosidase, urease, and arylsulfatase enzymes were higher in soils treated with the rapeseed residue than soils treated with the N, P, and K fertilisers. The eggshell additions at 1, 3, and 5% into soils treated with the rapeseed residue increased enzyme activity mainly resulting from N mineralisation, whereas no change in enzyme activity was observed in the soils treated with the NPK fertiliser. The combined use of the rapeseed residue and the eggshells can be beneficial to improve soil environment.     

饲料中新型持久性有机污染物分析方法与污染特征研究进展

饲料是养殖动物的主要食物来源,饲料中的持久性有机污染物(POPs)能够在养殖动物体内蓄积,从而影响动物源性食品安全,对人体健康构成潜在的危害.目前有关饲料中二英类等传统POPs的研究已较为深入,而饲料中新型POPs的污染也逐渐引起人们的关注.本文综述了现有文献关于饲料中多溴二苯醚(PBDEs)、六溴环十二烷(HBCD...     

Assessment of a large watershed in Brazil using Emergy Evaluation and Geographical Information System

Humanity's future depends on the preservation of natural ecosystems that supply resources and absorb pollutants. Rural and urban productions are currently based on chemical products made from petroleum, which are responsible for high negative impacts on the Biosphere. In order to prevent those impacts, efficient public policies seeking for sustainable development are necessary. Aiming to assess the load on the environment (considering the gratuitous contributions of natural systems—a donor's perspective) due to human-dominated process, a scientific tool called Emergy Evaluation has been applied in different production systems, including crops and farms. However, there is still a lack of emergy studies in the context of watersheds, probably due to the difficulty of collecting raw data. The present work aims to carry out an assessment of Mogi-Guaçu and Pardo watershed, through the combined use of Emergy Evaluation and Geographical Information System. The agricultural and natural land uses were considered, while urban areas were excluded. Emergy flows (expressed in seJ ha⁻¹ yr⁻¹) obtained for all agricultural and natural land uses were expanded for the whole watershed and the emergy indices were calculated. The results show that the watershed has: low renewability (%R = 32%); low capture of natural resources through high external economic investment (EYR = 1.86); low dependence on natural resources (EIR = 1.16); and moderate load on the environment (ELR = 2.08). Considering a scenario where sugar-cane crops, orchards and pasture areas are converted from conventional to organic management, watershed's emergy performance improved, reaching a new renewability of 38%, but it is still not enough to be considered sustainable.     

上海市沿海防护林下土壤养分、微生物及酶的典型相关关系

以上海市沿海防护林为研究对象,选择6种不同树种的防护林带,采集0～10、10～20、20～40、40～60cm四层土样为研究材料,运用典型相关分析法,对防护林地土壤养分因子、微生物因子和酶活性因子中每两组变量间的相关性进行了分析。结果表明：三组变量土壤养分、微生物、酶活性中,每两者之间均有显著的典型相关变量存在,而且基本能够代表变量总体相关信息;土壤养分和土壤微生物间的相关主要由全氮、速效磷含量与微生物生物量氮、微生物生物量碳和微生物生物量磷引起;土壤养分与土壤酶活性间的相关性主要由全氮、有效磷、水解氮含量与脲酶、蛋白酶活性的相关性引起;土壤微生物与土壤酶活性间的相关性主要是由微生物生物量氮、微生物生物量磷与脲酶、蛋白酶、碱性磷酸酶活性的相关性引起;不同林地不同土壤层次的养分、微生物及酶活性在各对典型变量上的聚集趋势可为防护林建设过程中的树种选择与土壤健康诊提供一定的依据。