人体尿液中磷系阻燃剂代谢产物检测方法的建立

本文构建了一种简单、快速、准确的液相色谱串联质谱(LC-MS/MS)测定人体尿液中6种磷系阻燃剂代谢产物的方法.尿液样品经β-葡萄糖醛酸酯酶/硫酸酯酶水解过夜后,使用Strata-X-AW小柱除去杂质,定容至150μL后使用LC-MS/MS进行分析.色谱的流动相为甲醇和10 mmol·L-1乙酸铵水溶液,梯度洗脱,用多反应通道监测(MRM)模式进行定性和定量分析.用本检测方法构建的含9个浓度梯度6种PFRs代谢产物(2.0、5.0、10.0、20.0、50.0、100.0、200.0、500.0、1 000.0 ng·m L-1)的标准曲线均线性关系良好(R20.998).双(1,3-二氯-2-丙基)磷酸酯(BDCPP),磷酸二苯酯(DPP),磷酸二丁酯(DBP),双(丁氧乙基)磷酸酯(BBOEP),双(1-氯-2-丙基)磷酸酯(BCPP)和双(2-氯乙基)磷酸酯(BCEP)检出限(LOQ)分别为0.23、0.23、0.62、0.38、0.38 ng·m L-1和0.12 ng·m L-1,加标回收率均在80%—107%间,平行样之间相对标准偏差(RSD)均小于20%.使用本文建立的方法对13位工人尿液样品中磷系阻燃剂代谢物浓度进行分析,BDCPP、DPP、DBP、BBOEP、BCPP和BCEP的平均浓度分别为1.8、2.3、6.2、0.4、0.5 ng·m L-1和12.9 ng·m L-1.BCEP检出率最高为100%,而DBP、BBOEP和BCPP的检出率低于50%.     

灰尘中有机磷系阻燃剂及其降解产物检测方法的建立

本研究建立了QuEChERS与液相色谱串联质谱(LC-MS/MS)联用方法,同时提取、净化灰尘样品中6种有机磷系阻燃剂(磷酸三苯酯(TPhP)、磷酸三丁酯(TnBP)、磷酸三(2-丁氧乙基)酯(TBOEP)、磷酸三(2-氯乙基)酯(TCEP)、磷酸三(2-氯丙基)酯(TCPP)、三(1,3-二氯-2-丙基)磷酸酯(TDCPP)及其降解产物(磷酸二苯酯(DPP)、磷酸二丁酯(DBP)、双(丁氧乙基)磷酸酯(BBOEP)、双(2-氯乙基)磷酸酯(BCEP)、双(1-氯-2-丙基)磷酸酯(BCPP)、双(1,3-二氯-2-丙基)磷酸酯(BDCPP)),上机检测.50 mg灰尘样品用3 mol·L~(-1)乙酸铵水溶液:乙腈(1∶1,V/V)混合溶液提取,加75 mg硫酸镁(MgSO_4)、25 mg N-丙基乙二胺(PSA)、25 mg碳18(C18)、25 mg石墨化碳黑(GCB)和75μL三乙胺进行净化,定容至1 mL后使用LC-MS/MS进行分析.色谱的流动相为甲醇和0.01 mol·L~(-1)乙酸铵水溶液,梯度洗脱,用多反应通道监测(MRM)模式进行定性和定量分析.该检测方法在2.0—1000.0 ng·mL~(-1)的范围内线性关系良好(R~20.996). OPFRs的加标回收率范围在92%—128%,相对标准偏差(RSDs)介于6.5%—9.5%.OPFRs降解产物的加标回收率范围在93%—129%,RSDs介于7.8%—14.9%.使用本文建立的方法对13例灰尘样品中OPFRs及其降解产物进行定量分析,TPhP、TnBP、TBOEP、TCEP、TCPP、TDCPP的平均浓度介于347.61—2197.58 ng·g~(-1),TPhP检出率最高,为100%,而TBOEP和TDCCP的检出率最低,为8%.DPP、DBP、BBOEP、BCEP、BCPP、BDCPP的平均浓度介于nd—1411.18 ng·g~(-1),DPP和BCEP检出率最高,为100%,而BBOEP的检出率最低,未被检出.     

珠江主干和东江河流表层沉积物中有机磷酸酯阻燃剂/增塑剂分布

有机磷酸酯阻燃剂/增塑剂(organophosphate esters,OPs)用量大、环境分布广泛、毒理效应显著,已成为环境领域关注热点。采用超声辅助提取结合固相萃取技术和气相色谱-质谱分析,研究珠江主干和东江河流表层样品中7种常见OPs含量水平与分布特征。结果表明,研究区域沉积物中OPs分布广泛,珠江主干∑7OPs范围为78.9~577 ng·g~(-1),主要污染物为磷酸三(丁氧基乙基)酯(TBEP),其次为磷酸三丁酯(TBP)和磷酸三(2-氯)乙酯(TCEP),均值分别为84.6 ng·g~(-1)、55.6 ng·g~(-1)和27.8 ng·g~(-1);东江河段沉积物中∑7OPs含量范围为24.0~293 ng·g~(-1),以磷酸三甲苯酯(TTP)、磷酸三苯酯(TPh P)和TBEP为主要污染物,平均浓度分别为55.6 ng·g~(-1)、32.7 ng·g~(-1)和17.5 ng·g~(-1)。以上结果揭示了珠江和东江沉积物中有机磷阻燃剂/增塑剂的浓度和分布是明显不同的,可能与不同来源的点源排放有关。     

有机磷酸酯对斑马鱼的早期神经毒性作用研究

国内外研究已证实,有机磷酸酯广泛分布于多种环境介质中,但目前仍缺乏足够的数据阐明有机磷酸酯具有早期神经毒性效应及其可能的毒性作用机制。本研究采用模式动物斑马鱼(Danio rerio)作为研究对象,选择了环境中3种典型的有机磷酸酯类化合物包括磷酸三苯酯(TPP)、2-乙基己基二苯基磷酸酯(EHDPP)和磷酸三(2-氯)乙酯(TCEP),从斑马鱼运动行为、氧化应激和神经发育关键基因的转录等方面阐述有机磷酸酯的早期神经毒性作用及可能的作用机制。研究发现,TPP(0.1和1 mg·L~(-1))、EHDPP(0.2和2 mg·L~(-1))和TCEP(0.5和5 mg·L~(-1))可能通过诱导氧化应激并下调神经发育关键基因(mbp和syn2a)的转录从而显著抑制斑马鱼的运动行为。本研究可以为有机磷酸酯类阻燃剂及其替代产品的生产、使用和危险度评估提供直接依据。     

液液提取-固相萃取-LC-MS/MS测定人体尿液中有机磷系阻燃剂及其二酯类代谢物

本研究基于液液提取和固相萃取技术建立了检测人体尿液中有机磷系阻燃剂(OPFRs)及其二酯类代谢产物(diesters)的前处理方法,采用液相色谱串联三重四极杆质谱(LC-MS/MS)进行定性定量分析.根据OPFRs与diesters理化性质的差异,尿液酶解后采用甲基叔丁基醚(MTBE)与二氯甲烷:正己烷(4∶1,V/V)混合液提取,有机相经Florisil固相萃取柱净化,乙酸乙酯洗脱后,测定OPFRs含量;水相过Strata-X-AW柱萃取,5%三乙胺/乙腈(V/V)洗脱后,测定diesters含量.在优化的实验条件下,OPFRs和diesters在相应浓度范围内呈良好线性关系,相关系数r介于0.9978—0.9997之间;尿液样品中OPFRs加标回收率平均值在72.4%—125%之间,RSD为0.62%—4.40%;6种diesters平均加标回收率为79.7%—126%,RSD介于2.20%—9.75%之间.本方法所需样品量少且能对OPFRs和diesters同时进行检测,方法的平行性好、结果可靠.使用该方法对15例尿液样品中的OPFRs与diesters含量进行分析发现,尿液中OPFRs检出率较低,7种OPFRs检出率均小于50%;6种diesters中仅双(丁氧乙基)磷酸酯(BBOEP)未在任何样品检出,其余5种diesters检出率介于33.3%—93.3%之间,其中磷酸二苯酯(DPHP)和双(1,3-二氯-2-丙基)磷酸酯(BDCIPP)检出率分别达93.3%和86.7%,是检出最高的两种化合物.     

上海城市污泥中有机磷酸酯阻燃剂/增塑剂分布的初步研究

采用超声提取、固相萃取和气相色谱质谱联用(GC-MS)分析技术,测定了12个上海市政污水处理厂外排污泥中的8种常见有机磷酸酯(OPs)的浓度水平与分布特征.所有污泥样品中检出多种OPs分布,OPs总含量范围为138—778 ng·g~(-1).主要污染物为三(1-氯-2-丙基)磷酸酯、三苯基磷酸酯、三-(2-氯乙基)磷酸酯(TCEP),浓度范围分别为LOD—206 ng·g~(-1)、8.82—52.9 ng·g~(-1)和7.12—65.7 ng·g~(-1).研究结果表明,生活污水和工业废水是OPs重要释放来源.因其显著毒性效应和持久性,TCEP被欧美等国禁用,但本研究污泥中广泛检出且含量水平较高(7.12—65.7 ng·g~(-1)),结果折射其高历史残留或持续使用.     

太湖西部入湖口沉积物中有机物分布及其潜在指示意义

太湖作为重要的工农业用水水源以及周边居民饮用水源,其水质安全受到高度关注。在太湖西部入湖口采集7个沉积物样品,研究了合成麝香、多环芳烃(PAHs)、有机磷酸酯阻燃剂/增塑剂(OPs)和有机氯农药(OCPs)含量水平和分布规律。研究结果表明,沉积物中多种污染物分布广泛,含量水平差异较大。其中,Σ15PAHs含量371 ng·g~(-1)~2.53$103ng·g~(-1),主要来源于生物质燃烧和化石燃料高温裂解;沉积物中检出4种多环麝香,主要组分为佳乐麝香(HHCB)(0.0792 ng·g~(-1)~1.17 ng·g~(-1))和吐纳麝香(AHTN)(0.123 ng·g~(-1)~1.29 ng·g~(-1)),它们指示了太湖水体已遭受一定程度生活污水输入影响;沉积物中Σ6OPs含量范围为1.63 ng·g~(-1)~21.9 ng·g~(-1),主要污染组分为磷酸三(2-氯丙基)酯(TCPP)和磷酸三(2-氯乙基)酯(TCEP),并呈现明显的点源排放特征;沉积物中六六六系列(HCHs)(0.310 ng·g~(-1)~1.11 ng·g~(-1))和滴滴涕系列(DDTs)(0.551 ng·g~(-1)~6.40 ng·g~(-1))主要来源于历史残留。位于太滆流域的几个入湖口沉积物中多种污染物含量多高于浙江省辖区3个入湖口沉积物。     

有机磷酸酯在成都市市/郊区剖面土壤及农作物中的分布及迁移

采用气相色谱-质谱联用仪定量分析了成都市区/郊区土壤和农作物中7种典型有机磷酸酯(OPEs)的浓度及分布.成都市市/郊区采土壤中Σ7OPEs的浓度范围为91.24—544.97 ng·g~(-1),郊区比市区OPEs污染严重.磷酸三丁酯(TnBP)、磷酸三丁氧乙酯(TBEP)和磷酸三异辛酯(TEHP)含量较高,而磷酸三(2,3-二氯丙基)酯(TDCPP)和磷酸三苯酯(TPhP)均未检出.OPEs在剖面土壤中存在纵向迁移,且迁移程度有差异.蚕豆易富集磷酸三氯丙酯(TCPP),芹菜对TBEP和TEHP的富集程度相对较高,牛皮菜易富集TEHP.     

4种典型有机磷阻燃剂对斑马鱼胚胎毒性及风险评价

近年来,有机磷阻燃剂(OPFRs)在各种环境介质中被广泛检出,已经成为全球关注的新型污染物。以斑马鱼(Danio rerio)胚胎为受试生物,研究了磷酸三苯酯(TPh P)、磷酸三正丁酯(Tn BP)、磷酸(1,3-二氯-2-丙基)酯(TDCPP)和磷酸三(2-氯丙基)酯(TCPP)4种典型有机磷阻燃剂对斑马鱼胚胎的急性毒性和慢性毒性。测定了斑马鱼胚胎孵化率、存活率、心率、体长、异常率、死亡率等终点指标。在此基础上,依据我国一些水域OPFRs检出情况,开展了初步的风险评价。结果显示,TPh P、TnBP、TDCPP和TCPP对斑马鱼胚胎的急性毒性96 h半数致死浓度(LC50)分别为1.90、2.27、2.32和14.1 mg·L-1,32 d慢性毒性无可见效应浓度(NOEC)值分别为0.03、0.05、0.05和1.00 mg·L-1,4种有机磷阻燃剂浓度与斑马鱼胚胎的孵化率、存活率、心率、体长呈负相关关系,与异常率呈正相关关系。TPh P、Tn BP、TDCPP和TCPP在我国一些重要水域中具有不同程度的环境风险,部分水域风险熵RQ值大于0.1甚至1,环境风险为中到高,需要引起足够重视。     

室内环境中通过灰尘摄入和手-口接触带来的阻燃剂人体暴露风险

本研究在广州市某高校随机选取17间大学宿舍进行灰尘取样,同时对居住于宿舍的32名在校学生进行手部擦拭取样.分析了室内灰尘和人手表面的阻燃剂(flame retardants, FRs)的含量水平和组成特征,并估算了灰尘摄入和手-口接触两种不同评估途径的日暴露量.多溴联苯醚(polybrominated diphenyl ethers, PBDEs)、磷酸酯阻燃剂(phosphorus flame retardants, PFRs)、德克隆(dechlorane plus, DP)、1,2-双(2,4,6-三溴苯氧基)乙烷(1,2-bis(2,4,6-tribromophenoxy)ethane, BTBPE)和十溴二苯乙烷(decabromodiphenyl ethane, DBDPE)在室内灰尘和手表面中均有检出.两种介质中的FRs组成相似,都主要包括BDE 209、DBDPE、PFRs,其中∑PFRs和DBDPE在两种介质中检出浓度最高,在灰尘中的中值浓度分别为1294 ng·g~(-1)和1751 ng·g~(-1),在手表面的中值浓度分别为277 ng·m~(-2)和41.7 ng·m~(-2).手-口接触摄入的FRs暴露量与灰尘摄入的FRs暴露量相当.在FRs的暴露风险评估中,手-口接触途径带来的FRs的暴露不容忽视.     

中国水稻土碳循环研究进展

文章首先分析了水稻土在碳循环研究中的地位和重要性，进而对我目水稻土碳循环的研究现状作了较为详尽的阐述，对其主要研究结论进行了深入的剖析。中国大而积的水稻土自1980年以来显示出有机碳库增加现象，说明水稻田对大气CO2可能产生汇效应。水耕熟化过程足有机碳的积累过程，水稻土的碳密度是早作土碳密度的2-3倍。水稻土的同碳能力与土壤的微团聚体的粒径有关。但对于水稻土中有机碳的分布和结合状态与农业管理措施、水稻土质量变化、农业生态环境变化的关系仍不清楚。因而建议就这一问题从土壤物理学、化学和生物学的相互作朋与土壤微团聚体中矿物质、有机质和微生物的相互结合关系的层面上进行多学科研究。同时提出了今后我困水稻土碳循环的重点研究方向和领域，即从整体和系统的角度来研究碳循环和平衡，从不同的时空区域来研究碳循环的过程和强度。     

Evaluating losses in ecosystem services in nature reserves in Sichuan,China

Nature reserves have developed rapidly over the decades in China and play a significant role in the function of ecosystem services. The function of ecosystem services in nature reserves, however, has tended to decline in recent years due to natural hazards and human activities. Based on land use, the variation of ecosystem services value (ESV) during 2000–2010 in national nature reserves in Sichuan was evaluated. We analyzed the comprehensive effects of natural disasters and human activities on the decline of ESVs. Total ESV in the national nature reserves in Sichuan was approximately 2741.35 million US$ in 2000, 2616.81 million US$ in 2005, and 2499.06 million US$ in 2010, representing a decrease of 242.29 million US$, or 8.84%, in the decade. Forestland, grassland, wetland, and water bodies played vital roles in the function of ecosystem services, with an aggregated ESV of 99% of the total. The largest proportion of the total ESV was the protection of biodiversity at 48.6%. ESV of all land use types and single ecosystem services continued to decline during 2000–2010. A mechanism of adaptable risk prevention should be established, and unreasonable human activities should be avoided to protect ecosystems and to improve the functions of ecosystem services.     

森林土壤固碳机理研究进展

全球碳平衡中,土壤有机碳储量为2000 Pg,植被碳储量500 Pg,大气碳储量785 Pg,土壤中有机碳变化是影响大气温室气体含量的重要因素。中国人工林总量世界第一,可以通过造林树种的选择,增加森林土壤的碳汇功能,它主要通过4种机理来实现,包括稳定性有机-矿物复合体的形成、持久性封存的深层碳的增加、耐分解有机物成份的积累、以及土壤团聚体结构中碳的物理性保护。中国近年来对木材的需求上升,导致大量短轮伐期人工林的种植,采伐、火烧炼山、施肥与整地等营林措施对土壤碳汇功能形成重大影响。因而,通过加强对中国人工林土壤固碳机理的研究,通过人为措施实现具有较强固碳能力的森林类型,从而提高人工森林生态系统的固碳能力,它对中国减排增汇战略具有重要意义,而加强对不同营林措施对碳汇功能影响的研究是中国当前面临的重大课题。     

Employment of passive sampling in monitoring indoor air quality in selected residences in a Tri-city area in Poland

Time-weighted average concentrations of selected volatile compounds were measured in chosen residences in a Tri-City area of Poland by means of passive sampling. The results were compared to those obtained by dynamic technique – sorption tubes filled with Tenax TA sorbent. Results obtained by employing the two techniques were similar. Total volatile organic compound (TVOC) parameters were also determined. An attempt was also made to evaluate the influence of outdoor air pollutants on indoor air quality.     

中国公众参与环境管理的研究

回顾了中国公众参与环境管理的发展历程,分析了公众参与环境管理存在的问题。针对公众参与环境保护管理的有效性的影响因子,例如主观因素、传统背景、时效因素及执行技巧等进行一系列的探讨,并根据公众参与计划的设计构思、公众参与计划的关键两方面的讨论,提出增加公众参与环境保护管理有效性的一些建议。     

Environmental education in comprehensive schools in Greece

The new institution of comprehensive high school, in Greece today, aims to relate the school with the natural, social, economical and cultural environment. In this frame of process, interrelation and dynamic contact of school with the holistic environment, the subject “Ecology and Environment”; of the 2nd class (16–17 years old), informs, sensitizes and activizes the anxious young generation. The textbook of the subject determines and analyzes the human impact and their consequences to the natural ecosystems. In the total content there are also numerous examples from the natural, man‐made and cultural environment of Greece.     

生物扰动在水层-底栖界面耦合中的作用

综合评述了生物扰动在水层-底栖界面耦合中的作用研究进展和热点问题,并进行了展望。国际上十分重视水层-底栖界面耦合过程的研究并已有一定基础,生物扰动作为海洋生态学的重要内容之一早在20世纪50—60年代就已开展了工作,但直到10余年前才真正开始定量研究,进入了实验模拟、现场观测与建立模型相结合的新阶段。国内的生物扰动研究尚处于起步阶段,加上技术方法落后,一直未能取得突破性进展。目前国内外关于水层-底栖界面生物扰动效应研究基本上都在海洋中开展,尤其在河口、近岸和浅海水域进行,湖泊和河流研究明显薄弱。作为水生态动力学的重要分支和前沿领域,生物扰动研究具有广阔前景。急需针对我国水域特点,引进先进的现场观测和室内测试手段,进一步揭示水层-底栖界面耦合过程中的生物扰动机制,更精准和更详细地掌握水域中各种物质的生物地球化学循环的全过程,为控制水体内源污染释放、富营养化治理和生态建模等提供科学依据。     

Variation in male courtship costs in butterflies

A cost of mating is common to both sexes but has predominantly been examined in females. In species where males provide resources to females at copulation, male mating costs are expected to be high as nutrient provisioning enhancing female fecundity is assumed to carry costs. In addition, males frequently court females prior to mating, which is known to carry survival costs to both sexes. However, the magnitude and basis of variation in males’ mating costs remains largely unknown. Here, I examine the effect of nutrient provisioning and courtship on male longevity across full-sib families in the paternally investing green-veined white butterfly, Pieris napi. Copulating males suffered a survival cost as did courting males prevented from copulating, indicating the courtship component of mating is costly. Male P. napi release aphrodisiacs during courtship to promote mating, indicating that these compounds may also be costly to produce. Contrary to expectation, nutrient provisioning was not associated with reduced survival relative to males only allowed to court females, although it is possible that this could be masked by the potentially elevated courtship rates of courting males relative to mating males. Families differed in magnitude of reduced male survivorship, indicating a likely genetic basis to variation in costs of courtship and copulation. Male weight was unrelated to longevity and mating success, whereas longevity strongly influenced male mating success, indicating lifespan is an important male fitness trait in this species.     

Is the antipredatory response in behaviour reflected in stress measured in faecal corticosteroids in a small rodent?

Predation risk has been shown to alter various behaviours in prey. Risk alters activity, habitat use and foraging, and weight decrease might be a consequence of that. In mammals, studies on physiological measures affected by risk of predation, other than weight, are rare. We studied in two separate laboratory experiments foraging, hoarding behaviour and expression of stress measured non-invasively from the faeces in the bank vole (Clethrionomys glareolus), a common boreal rodent. Voles were exposed to predation risk using odours of the least weasels (Mustela nivalis nivalis). Distilled water served as control. In the first experiment, we found that foraging effort, measured as sunflower seeds taken from seed trays filled with sand, was significantly lower in trays scented with weasel odour. Both immediate consumption of seeds and hoarding were affected negatively by the weasel odour. Females hoarded significantly more than males in autumn. In the second experiment, the negative effect of weasel odour on foraging was consistent over a 3-day experiment, but the strongest effect was observed in the first night. Foraging increased over the time of the experiment, which might reflect either energetic compensation during a longer period of risk, predicted in the predation risk allocation hypothesis, or habituation to the odour-simulated risk. Despite decreased foraging under predation risk, stress measured as corticosteroid metabolite concentration in vole faeces was not affected by the weasel odour treatment. In conclusion, we were able to verify predation-risk-mediated changes in the foraging effort of bank voles but no physiological stress response was measured non-invasively, probably due to great individual variation in secretion of stress hormones.