残渣吸着对消化道中土壤多环芳烃生物可给性体外测定的影响

用体外模拟方法研究了土壤中多环芳烃在消化过程中的释放,并验证了如下假设:消化过程释放出来的多环芳烃部分吸着在消化残渣相中,且该吸着可以影响多环芳烃生物可给性测定结果,研究结果表明,经消化释放出来的多环芳烃可以部分吸着在消化固相残渣中,就有机碳含量从2.87%到0.63%的四种土壤中的平均情况而言,多环芳烃残余固相上的吸着量占总可给态量的比率分别为:43.6%±14.3%(二氢苊),29.8%±24.6%(苊),43.1%±22.9%(芴),34.1%±25.8%(菲),14.0%±16.2%(蒽),25.2%±15.9%(荧蒽),33.4%±23.1%(芘),30.7%±26.6%(苯并葸)和29.1%±23.4%(芑),显然,忽略吸着现象将显著低估实际消化率,如果对吸着进行定量校正,则总多环芳烃的消化率分别从校正前的18.9%,12.2%,22.8%和33.4%增长到29.0%,29.3%,41.9%和37.6%,提升幅度在4.21%到10.1%之间.     

土壤中锁定残留芘在体外消化系统中的生物可给性（Oral Bioaccessibility of Bound Residue of Pyrene in Contamination Soils Determined by an in Vitro Gastrointestinal Model）

体外消化过程可能导致土壤中憎水有机污染物提取量增加.论文采用3种有机质含量不同的土壤进行体外消化实验,目的在于验证如下假设:土壤中部分锁定残留芘可以在人体消化系统中释放出来,若不考虑这部分贡献,常规提取方式获得的土壤污染浓度可能低估污染土壤口摄风险.研究结果证实:经体外消化的土壤的总芘提取量显著高于未经消化样品,其差别与土壤有机质含量有关.消化液中的胆汁盐是造成锁定残留芘释放的关键成份.在特定范围(2~20mg·mL-1)内,提取效率不受胆汁盐浓度影响.胆汁盐作用下锁定残留芘的释放为一次动力学过程.     

农村室内薪柴燃烧的颗粒物和炭黑排放因子

室内薪柴燃烧是大气污染的重要来源,其排放的污染物对气候变化和人体健康都有很大影响。对该来源排放量的可靠估算是进行排放效应分析和合理控制的重要前提,而估算的可靠性主要取决于燃料消耗量和排放因子的准确性。目前,我国针对农村柴灶薪柴燃烧颗粒物排放因子的测定数据很少,变异很大,不足以支持可靠的排放清单估算。测定了9种薪柴(枫桦、兰考泡桐、黑杨、大叶风杨、楝树、枣树、柿树、桑树和桃树)在中国北方典型农村炉灶中燃烧产生的颗粒物(PM)、有机碳(OC)和元素碳(EC)的排放因子。受燃料种类、性质和燃烧条件的影响,测得的排放因子差别较大。9种薪柴各自的PM、EC和OC的排放因子变化范围分别为(0.74±0.13)～(6.23±1.47)g.kg-1,(0.10±0.06)～(0.97±0.28)g.kg-1和(0.14±0.03)～(3.81±0.92)g.kg-1(以干质量计)。全部薪柴的PM、EC和OC的排放因子均值和标准差分别为(2.58±2.15)、(0.29±0.31)和(0.98±1.24)g.kg-1。室内薪柴燃烧PM、EC和OC排放因子之间呈显著的相关性关系。各种薪柴燃烧排放的颗粒物粒径分布相似,均以细颗粒物为主,PM2.1占PM10总质量的90%以上。此外,除EC排放因子外,薪柴燃烧的PM和OC排放因子与校正燃烧效率显著负相关(P<0.05)。细颗粒物组分PM2.1与校正燃烧效率显著负相关(P<0.05),与燃料含水量显著正相关(P<0.05)。     

盐生植物在盐渍土壤改良中的作用

盐生植物盐爪爪〔Kalidiumfoliatum (Pall.)Moq.〕、盐地碱蓬 (SuaedasalsaL .Pall)、中亚滨藜 (AtriplexcentralasiatieaIljin)、西伯利亚白刺 (NitrariasibiricaPall) ,在中国禹城地区〔φ(N) =36°5 5′,λ(E) =116°40′〕含盐量较高 (1%～ 1.3%)的试验田中分别种植 .出苗后定苗 ,株密度n =80m-2 ,小区面积为 4m2 ,每种植物 3个重复 .种植前分别测定土壤Na+ 含量 ,N、P、K含量 ,有机质含量 ,细菌和真菌数量 .萌发后 15d测定植株干重、植株Na+ 含量 .在花芽形成期收获 ,再测定植物干重和植株Na+ 含量 ,以及土壤Na+ 含量 ,N、P、K含量 ,有机质含量 ,细菌和真菌数量 .结果发现 ,盐渍土壤种植 4种盐生植物 1个季度后 ,土壤Na+ 含量显著降低 ,每季盐爪爪从土壤中吸收Na+ 量 934 5 .6kg/hm2 ,盐地碱蓬吸收Na+ 量 6 85 1.4kg/hm2 ,西伯利亚白刺吸收 6 0 19.2kg/hm2 ,中亚滨藜吸收 6 0 98.4kg/hm2 .土壤有机质 ,N、P、K以及细菌和真菌数量也有不同程度的增加 .这再次证明 ,盐生植物是一类良好的吸盐植物 .并对盐渍土壤种植盐生植物后Na+盐降低、土壤肥力和微生物数量增加的原因进行了讨论 .表 7参 13     

不同生态类型富营养化湖泊沉积物中有机质赋存形态

以藻型湖泊(太湖)、草藻型湖泊(南四湖)、草型湖泊(白洋淀)湖泊沉积物为研究对象,采集了11个表层沉积物样品,测定沉积物中总氮(TN)和总磷(TP)含量并利用物理分组方法,研究了3种不同生态型湖及同一湖泊不同区域沉积物中总有机质(OM)、轻组有机质(LFOM)和重组有机质(HFOM)的赋存特征.结果表明,南四湖沉积物中总氮、总磷和总有机质含量显著高于太湖和白洋淀;尽管太湖、南四湖和白洋淀沉积物中总有机质含量较高,但是轻组有机质(LFOM)含量较低,分别占总有机质的0.95%—1.08%、0.21%—1.37%和1.4%—1.78%;重组有机质(HFOM)含量较高,分别占总有机质的83.83%—87.4%、94%—98.98%和88.2%—98.3%,表明3种不同生态型湖泊沉积物中所含有机质绝大部分为难分解的重组有机质,轻组有机质基本矿化分解.相关性分析表明,轻组有机质(LFOM)、重组有机质(HFOM)与总有机质(OM)之间均呈现显著正相关关系.     

土壤中水溶性有机碳与铜的相互影响

通过向土壤溶液中加入Ｃｕ２＋和可溶性有机碳(ＤＯＣ),研究它们之间的相互作用．结果发现,加入铜可以显著改变土壤水溶性有机碳(ＷＳＯＣ)的吸着平衡,并降低了其水溶性．影响程度在０．８ｍｍｏｌ·ｌ－１Ｃｕ以下随铜浓度的增加而增加．加入０．５ｍｍｏｌ·ｌ－１铜的土壤中 ＷＳＯＳ含量从 ０．２７ｍｇ Ｃ·ｇ－１降至０．０４７ｍｇ Ｃ·ｇ－１,吸着系数从６．６×１０－３ｌ·ｇ－１降至３．３×１０－３ｌ·ｇ－１．另一方面,用Ｆｒｅｕｎｄｌｉｃｈ方程描述铜离子在土壤中的吸附行为(液相浓度单位取ｍｍｏｌ·ｌ－１,固相浓度取ｍｍｏｌ·ｇ－１土),ｋ＝９．ｌ×１０－３;ｎ＝３．４０． 加入ＤＯＣ后,ｋ＝９．２×１０－３;ｎ＝３．６６,没有明显改变土壤对铜的吸附性能．加入小同浓度的ＤＯＣ,结果仍说明该浓度范围内ＤＯＣ(＜８ｍｇ Ｃ·ｌ－１)的加入没有明显改变土壤对铜的吸附性能．     

2种无机洗脱剂对矿区污染土壤中铅、镉的洗脱研究

选用HCl和CaCl2 2种无机洗脱剂对矿区重金属污染土壤进行化学洗脱试验,分析比较了2种洗脱剂对土壤中Pb、Cd的洗脱效果,并探讨了洗脱剂浓度、洗脱时间、温度、固液比、洗脱次数对土壤中Pb、Cd洗脱效果的影响.结果表明,对于土壤中Pb的洗脱,HCl的效果优于CaCl2,其洗脱率分别为26.0% ～68.2%和14.6% ～48.7%;而对于土壤中Cd的洗脱,CaCl2优于HCl,其洗脱率分别为30.7% ～54.6%和24.2% ～42.6%.在各影响因素中,洗脱剂浓度对土壤中Pb的洗脱有显著影响,而洗脱次数对土壤中Cd的洗脱有显著影响,其他因素对Pb、Cd的洗脱均无显著影响.洗脱土壤中Pb的最佳操作条件为:HCl 200 mmol·L-1、时间240 min、温度20 ℃、m(固)∶V(液)=1∶15、洗脱2次;洗脱土壤中Cd的最佳操作条件为:CaCl2 50 mmol·L-1、时间240 min、温度35 ℃、m(固)∶V(液)=1∶20、洗脱4次.     

氯化二丁基锡对小鼠外周血液中睾丸酮和雌二醇含量的影响

用放射免疫法分别测定了DBTCl对妊娠d6雌小鼠和成年雄小鼠外周血液中雌二醇和睾丸酮水平的影响.每天按小鼠体重一次腹腔注射0.025～0.400μg/kgd-1DBTCl,共染毒7d.实验条件为(22±2)℃和光暗=12h12h.结果表明,处理组睾丸酮和雌二醇的含量随处理剂量的增加而增加,当w（DBTCl）≥0.05μg/kg时,二者呈明显的剂量-效应关系.雌二醇含量的增加比睾丸酮更为显著CK雄性小鼠睾丸酮浓度为（2.88±0.72）ng/mL,在0.40μg/kg剂量组达到(9.95±2.5)μg/mL时,约为CK的3.5倍;而CK和0.40ng/kg剂量组妊娠小鼠雌二醇浓度分别为(30.32±5.43)ng/mL和(287.57±51.13)ng/mL,相差约9.5倍.文中还就DBTCl对小鼠血液中激素含量的影响机理进行了初步探讨.图1表2参20     

灌溉水质与土壤有机质累积的关系

为了确定长期使用污染水灌溉对土壤有机物质累积的影响,在陕西交口抽渭灌区采集土壤样品,并以气候条件、土壤条件以及耕作制度基本一致,长期用井水灌溉的土壤作为对照,测定了土壤有机质的质量分数及其组成,其结果显示:长期用污染的渭水灌溉,土壤有机质主要在耕层(020 cm)极显著增加,且增加部分主要是活性有机质,非活性有机质基本不受影响;耕层土壤中的胡敏酸及富啡酸质量分数均极显著增加,土壤熟化程度有略微提高.灌溉水质几乎不能改变与气候生态条件和土壤条件相协调的非活性有机质的"生态极限含量".     

模拟降水量变化对华西雨屏区天然常绿阔叶林土壤酶活性的影响

土壤酶是土壤生物化学过程的参与者,在森林土壤有机物的矿质化和腐殖化过程中起着重要作用;研究降水量变化对土壤酶活性的影响对于揭示全球降水格局变化背景下土壤有机物的矿化与腐殖质的合成过程具有重要意义.从2013到2015年,以华西雨屏区天然常绿阔叶林为研究对象,通过布设减雨架和人工喷洒方式对降水量进行调控,设置了对照(Ctr)、减少10%降水量(Dr)和增加10%降水量(W)3种处理,研究降水量变化对土壤酶活性和有机质含量的影响.结果表明:Dr处理下土壤蔗糖酶、脲酶和酸性磷酸酶活性分别提高了4.0%、4.3%和2.1%,过氧化氢酶、过氧化物酶和多酚氧化酶活性分别降低了3.9%、5.9%和10.3%;W处理下蔗糖酶、脲酶和酸性磷酸酶活性分别降低了12.4%、6.4%和14.4%,过氧化氢酶、过氧化物酶和多酚氧化酶活性分别提高了5.8%、3.9%和3.8%.多元线性回归分析表明,土壤微生物生物量碳(MBC)、NH_4~+-N含量和含水量是土壤酶活性变异的主导因子.Dr处理降低了土壤有机质含量,而W处理提高了土壤有机质含量.相关性分析表明,土壤有机质含量与土壤水解酶活性呈负相关关系,与氧化还原酶活性呈正相关关系.上述结果说明降水量变化通过影响土壤理化性质改变了华西雨屏区天然常绿阔叶林的土壤酶活性,进而影响了土壤有机质含量,对土壤有机质的转化过程产生了重要影响.(图2表5参47)     

The role of soil humic and fulvic acid in the sorption of endosulfan (alpha and beta)

The sorption behaviour of alpha- and beta-endosulfan in soil organic matter was investigated using standard soil humic acid (HA) and soil fulvic acid (FA) with a modified solubility enhancement method and a dialysis bag technique. For HA, all the experiments were conducted at an ionic strength of 0.001 mol/L, in both the presence and absence of calcium and at an ionic strength of 0.01 mol/L. For FA, the experiments were conducted at two ionic strengths: 0.001 mol/L (with calcium) and 0.01 mol/L. This study is the first to describe the striking differences in the sorption behaviours of the two stereoisomers of endosulfan in HA and in FA. The sorption coefficients of alpha-endosulfan in HA and FA were significantly higher than those of beta-endosulfan. Beta-endosulfan has comparable sorption coefficients (1.5–5.4 L/g) in HA and in FA. Ionic strength and the presence of calcium have no significant effect on the sorption of beta-endosulfan in HA. However, calcium can significantly (p=0.01) enhance the solubility of alpha-endosulfan in HA. Changes in ionic strength by one order of magnitude also affect the solubility of alpha-endosulfan in HA. The sorption coefficients of alpha-endosulfan in HA (10–36 L/g) were greater than those in FA (9–14 L/g). The chirality of the alpha-isomer was hypothesised to be the primary reason behind its higher sorption in soil organic matter relative to the beta-isomer. In the presence of dissolved HA and FA found in natural soil environments, solubility of endosulfan can be increased by five times than the aqueous solubility of endosulfan without HA and FA.     

The environmental fate of thymol,a novel botanical pesticide,in tropical agricultural soil and water

In this study, the environmental fate of thymol, including hydrolysis, aqueous photolysis, soil sorption and soil degradation, was studied under conditions that simulated the tropical agricultural environment. This study was undertaken to supply basic information for evaluating the environmental risks of applying this new botanical pesticide to tropical crop production. The results showed that the hydrolysis of thymol was pH-dependent and accelerated by acidic conditions and high temperatures. However, the hydrolysis rate was far lower than the aqueous photolysis rate, indicating that direct photolysis is an important dissipation pathway for thymol in water. The sorption of thymol by three tropical soils was consistently well described by the Freundlich model, and the sorption coefficients increased in the order sandy soil < loamy soil < clay soil, a characterization that depended on the organic carbon contents of the soil. The soil degradation rate of thymol decreased in the order sandy soil > loamy soil > clay soil, which has a negative correlation with the sorption of thymol in soils. We concluded that the degradation rates of thymol in tropical soil and water are fast: thymol in water is photodegraded (50%) by sunlight within 28 h, and the thymol in soils is degraded (50%) within 8.4 d. Therefore, the environmental risk to the surrounding soils and water of thymol application for tropical crop production is low.     

Residues and sources of organochlorine pesticides in soils of elementary schools and communities in Wenchuan 5.12 Earthquake-affected areas

The disinfectants and pesticides extensively used after Wenchuan 5.12 Earthquake on May 12, 2008 (so-called Wenchuan 5.12 Earthquake), for epidemic prevention purpose can raise great concerns of environmental pollution and potential personal exposure. To investigate the soil pollution caused by the intensive application in earthquake-affected areas, surface soil samples from two elementary schools, two communities and two background areas were collected in Beichuan County and Dujiangyan City once per location in spring and in autumn in 2011 and then analyzed by gas chromatography/mass spectrometry for organochlorine pesticides (OCPs). The results showed serious soil pollution of hexachlorocyclohexanes (HCHs, 0.05–60.05 ng/g) and dichloro-diphenyl-trichloroethane (DDTs, 0.06–35.79 ng/g) in the study areas compared with Wolong Nature Reserve (0.03–0.81 ng/g for HCHs and 0.02–0.40 ng/g for DDTs). The concentrations of most OCPs in soil of Beichuan County (e.g., 0.10–60.05 ng/g for HCHs and 0.17–35.79 ng/g for DDTs) were much higher than those of Dujiangyan City (e.g., 0.05–20.58 ng/g for HCHs and 0.06–10.69 ng/g for DDTs). In Beichuan County, the highest concentrations of HCHs and DDTs were found in the elementary school. In Dujiangyan City, the highest concentrations of HCHs and DDTs were found in the elementary school and the community, respectively. The concentrations of HCHs and DDTs were generally higher in spring than those in autumn. The predominant species (γ-HCH in ∑HCHs and 4,4′-DDT in ∑DDTs) and specific ratios suggested new inputs of lindane and technical DDT in the study areas. Therefore, continuous soil monitoring and possible intervention would be recommended to minimize local residents’ exposure to these toxic chemicals.     

A novel extraction method for analysing available sulfamethoxazole in soil

A novel extraction method was established to determine the water-extractable (available) content of sulfamethoxazole (SMX) in soil. The SMX imprinted polymers (MIPs) were synthesised and the performance was evaluated by Fourier transform infrared spectroscopy, scanning electron microscopy and binding experiments. Results showed that the MIPs exhibited good selectivity for SMX, so the MIPs were applied as a sorbent. SMX in soil was extracted by water, sorbed from the extract to MIPs and analysed with a high performance liquid chromatography (HPLC) after its desorption from MIPs. Meanwhile, the classic organic solvent extraction was employed to measure the total SMX content in soil. Results showed that when SMX level in spiked soils varying from 1.0–500?μg?kg^?1, the observed recoveries of available SMX contents ranged from 63.27?±?3.11% to 82.11?±?2.77% (n?=?3), while the total SMX varied between 89.59?±?1.65% and 97.64?±?3.92% (n?=?3). The detection limit of the developed method for SMX in soils was 0.05?μg?kg^?1. Available SMX contents in five field soil samples ranged from 0.13 to 4.14?μg?kg^?1, which were only 0.35–25.40% of the respective total SMX contents. Results from this study manifest the importance of the extents of SMX immobilisation with different soils for assessing SMX's ecological and human health risks.     

太原市土壤六六六和滴滴涕的暴露格局及健康风险

为研究六六六(HCHs)和滴滴涕(DDTs)在太原市不同功能区土壤中的暴露格局、来源以及对周围人群的健康风险,在太原市化工区、灌区、矿区、生态区周边荒地土壤中进行采样,分析测定了土壤中HCHs和DDTs含量,根据太原市人群实际情况的暴露参数和USEPA的部分参数,对土壤HCHs和DDTs的健康风险进行评价。结果表明:1)太原市表层土壤中HCHs的平均含量大小依次为化工区>灌区>矿区>生态区;DDTs平均含量的大小依次为化工区>灌区>矿区>生态区,仅6%的HCHs和3%的DDTs和的平均残留水平均高于我国土壤质量标准一级标准,但均不超过二级标准值;2)土壤中HCHs残留主要源于历史上林丹的使用,DDTs残留则来源于历史和新污染源的共同影响;3)太原市表层土壤HCHs和DDTs致癌风险大小为化工园区>矿区>灌区>生态区。非致癌风险大小为化工区>矿区>灌区>生态区。3种暴露途径的在不同功能区的健康风险贡献率大小均为经口摄入>呼吸吸入>皮肤接触;综合来看太原市表层土壤中的HCHs和DDTs并未对人类造成非致癌风险,但有一定的致癌风险。本文的研究结果可为太原市土壤质量评价和环境污染防治提供科学指导,并对太原市人群的健康风险防治提供依据。     

久效磷在海洋沉积物上的吸附行为

研究了久效磷在海洋沉积物上的吸附行为，发现其吸附行为主要受沉积物有机质的影响，沉积物有机质的分配作用对久效磷的吸附起主要作用，在实验浓度范围内，吸附行为很好地服从线性吸附等温式，因而其吸附行为较为简单，海水的离子强度对其吸附行为影响很大，海水中分配系数明显高于淡水，温度对其吸附行为也起一定的作用，分配系数随着温度的升高略微减小。     

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbonnormalized distribution coefficient (K _oc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (< 20%), while the 375°C heating fractions were the highest (up to 85%).     

Concentrations and classification of HCHs and DDTs in soil from the lower reaches of the Jiulong River, China

Soil is an important source to other environmental media and organisms for organochlorine pesticides (OCPs) bioaccumulation. Twenty-four representative surface soil samples were collected from the lower reaches of the Jiulong River, China, in 2009. The concentrations of hexachlorocyclohexane isomers (HCHs) ranged from 0.38 to 39.52 ng·g^?1, with a mean value of 9.51 ng·g^?1. The concentrations of dichlorodiphenyltrichloroethanes (DDTs) and their metabolites were within the ranges of 0.94–700.99 ng·g^?1, with a mean value of 71.17 ng·g^?1. The concentrations of HCHs and DDTs in the soil were lower than the first grade level (50 ng·g^?1) of the Chinese Environmental Quality Standard (GB15618-1995). Hierarchical Cluster Analysis (HCA) and Pearson’s bivariate Correlations Analysis (PCA) were used to analyse the distribution and contamination levels of OCPs in this region. The results showed that DDTs were the major contaminants and there were no significant correlations between various OCPs concentrations and the total organic carbon (TOC) contents. A significant positive correlation was observed between HCHs and DDTs (p<0.01), which indicates that HCHs and DDTs may have similar sources and fate in the study area.     

多环芳烃在全土及其碱提残余物上的吸附行为

以菲和芘为代表性化合物,采用8种有机质含量不同的天然全土样品及其碱提残余物进行吸附实验,并利用不同吸附模型进行数据拟合,藉以探讨有机质含量对土壤吸附行为的影响.结果表明,Freundlich吸附模型的非线性指数n都小于1,显示全土和碱提残余物在多环芳烃的吸附过程中表现出非线性特征.菲和芘的吸附行为随土壤有机质含量不同而变化,碱提残余物的吸附能力强于全土,两者吸附行为的差异主要归因于土壤有机质含量和性状的区别.     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.