210Po in the marine environment with emphasis on its behaviour within the biosphere

The distribution and behaviour of the natural-series alpha-emitter polonium-210 in the marine environment has been under study for many years primarily due to its enhanced bioaccumulation, its strong affinity for binding with certain internal tissues, and its importance as a contributor to the natural radiation dose received by marine biota as well as humans consuming seafoods. Results from studies spanning nearly 5 decades show that ²¹⁰Po concentrations in organisms vary widely among the different phylogenic groups as well as between the different tissues of a given species. Such variation results in ²¹⁰Po concentration factors ranging from approximately 10³ to over 10⁶ depending upon the organism or tissue considered. ²¹⁰Po/²¹⁰Pb ratios in marine species are generally greater than unity and tend to increase up the food chain indicating that ²¹⁰Po is preferentially taken up by organisms compared to its progenitor ²¹⁰Pb. The effective transfer of ²¹⁰Po up the food chain is primarily due to the high degree of assimilation of the radionuclide from ingested food and its subsequent strong retention in the organisms. In some cases this mechanism may lead to an apparent biomagnification of ²¹⁰Po at the higher trophic level. Various pelagic species release ²¹⁰Po and ²¹⁰Pb packaged in organic biodetrital particles that sink and remove these radionuclides from the upper water column, a biogeochemical process which, coupled with scavenging rates of this radionuclide pair, is being examined as a possible proxy for estimating downward organic carbon fluxes in the sea. Data related to preferential bioaccumulation in various organisms, their tissues, resultant radiation doses to these species, and the processes by which ²¹⁰Po is transferred and recycled through the food web are discussed. In addition, the main gaps in our present knowledge and proposed areas for future studies on the biogeochemical behaviour of ²¹⁰Po and its use as a tracer of oceanographic processes are highlighted in this review.     

Polonium (210Po) and lead (210Pb) in marine organisms and their transfer in marine food chains

The determination of ²¹⁰Po and ²¹⁰Pb was performed in marine organisms from the seashore to abyssal depths, encompassing a plethora of species from the microscopic plankton to the sperm whale. Concentrations of those radionuclides ranged from low values of about 5 × 10⁻¹ Bq kg⁻¹ (wet wt.) in jellyfish, to very high values of about of 3 × 10⁴ Bq kg⁻¹ (wet wt.) in the gut walls of sardines, with a common pattern of ²¹⁰Po > ²¹⁰Pb.These radionuclides are primarily absorbed from water and concentrated by phyto- and microzooplankton, and then are transferred to the next trophic level along marine food chains. Investigation in epipelagic, mesopelagic, bathypelagic and abyssobenthic organisms revealed that ²¹⁰Po is transferred in the marine food webs with transfer factors ranging from 0.1 to 0.7, and numerically similar to those of the energy transfer in the marine food chains. As ²¹⁰Po preferentially binds to amino acids and proteins, its transfer in food chains likely traces protein transfer and, thus, ²¹⁰Po transfer factors are similar to ecotrophic coefficients. ²¹⁰Pb is transferred less efficiently in marine food chains and this contributes to increased ²¹⁰Po:²¹⁰Pb activity ratios in some trophic levels.     

Correlation and toxicological inference of trace elements in tissues from stranded and free-ranging bottlenose dolphins (Tursiops truncatus)

The significance of metal concentrations in marine mammals is not well understood and relating concentrations between stranded and free-ranging populations has been difficult. In order to predict liver concentrations in free-ranging dolphins, we examined concentrations of trace elements (Al, As, Ba, Be, Cd, Co, Cu, Fe, Li, Mn, Ni, Pb, Sb, Se, Sn, total Hg (THg), V, Zn) in skin and liver of stranded bottlenose dolphins (Tursiops truncatus) from the South Carolina (SC) coast and the Indian River Lagoon, Florida (FL) during 2000-2008. Significantly higher concentrations of Zn, Fe, Se, Al, Cu and THg were found in skin while liver exhibited significantly higher Cu, Fe, Mn and THg concentrations for both study sites. Mean skin concentrations of Cu and Mn were significantly higher in SC dolphins while higher concentrations of THg and V were found in FL dolphins. In addition, liver tissues in SC dolphins exhibited significantly higher As concentrations while higher Fe, Pb, Se, THg, and V levels were found in FL dolphins. Two elements (Cu and THg) showed significant age-related correlations with skin concentration while five elements (Cu, Se, THg, Zn and V) showed age-related correlations with liver concentrations. Geographic location influenced age-related accumulation of several trace elements and age-related accumulation of THg in hepatic tissue was observed for both sites to have the highest correlations (r² = 0.90SC; r² = 0.69FL). Mean THg concentration in liver was about 10 times higher in FL dolphins (330 μg g⁻¹ dw) than those samples from SC dolphins (34.3 μg g⁻¹ dw). The mean molar ratio of Hg to Se was 0.93 ± 0.32 and 1.08 ± 0.38 for SC and FL dolphins, respectively. However, the Hg:Se ratio varied with age as much lower ratios (0.2-0.4) were found in younger animals. Of the 18 measured elements, only THg was significantly correlated in skin and liver of stranded dolphins and skin of free-ranging dolphins from both sites suggesting that skin may be useful in predicting Hg concentrations in liver tissue of free-ranging dolphins. Results indicate that 33% of the stranded and 15% of the free-ranging dolphins from FL exceed the minimum 100 μg g⁻¹ wet weight (ww) (∼400 dw) Hg threshold for hepatic damage while none from SC reached this level. Hepatic concentrations of As in SC dolphins and V in FL dolphins were also highly correlated with skin concentrations which may have some regional specificity predictive value. The present study provides the first application of trace element concentrations derived from stranded bottlenose dolphins to predict liver concentrations in free-ranging populations.     

The degradation of chlorpyrifos and diazinon in aqueous solution by ultrasonic irradiation: effect of parameters and degradation pathway

In this paper, elimination of two types of organophosphorus pesticides (OPPs), chlorpyrifos and diazinon spiked in aqueous solution by ultrasonic irradiation was investigated. Results showed that chlorpyrifos and diazinon could be effectively and rapidly degraded by ultrasonic irradiation, and the degradation of both pesticides was strongly influenced by ultrasonic power, temperature and pH value. Furthermore, two and seven products for the degradation of chlorpyrifos and diazinon formed during ultrasonic irradiation have been identified by gas chromatography-mass spectrometry, respectively. The hydrolysis, oxidation, hydroxylation, dehydration and decarboxylation were deduced to contribute to the degradation reaction and the degradation pathway for each pesticide under ultrasonic irradiation was proposed. Finally, the toxicity evaluation indicated that the toxicity decreased for diazinon solution after ultrasonic irradiation, but it increased for chlorpyrifos solution. The detoxification of OPPs by ultrasonic irradiation was discriminative.     

Surface chemistry of a pine-oil cleaner and other terpene mixtures with ozone on vinyl flooring tiles

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O₃), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O₃ (100 ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol + O₃ reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol + O₃ reaction products were the prominent species that were also observed in the POC/O₃ surface experiments. Furthermore, α-terpineol + O₃ reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions.     

Metallothioneins failed to reflect mercury external levels of exposure and bioaccumulation in marine fish--considerations on tissue and species specific responses

The suitability of metallothioneins (MT) in fish as biomarker of exposure to mercury has been questioned. Therefore, this study aimed at investigating the relationship between external levels of exposure, mercury accumulation and MT content, assessing species and tissue specificities. Two ecologically different fish species - Dicentrarchus labrax and Liza aurata - were surveyed in an estuary historically affected by mercury discharges. Total mercury (T-Hg) and MT content were determined in gills, blood, liver, kidney, muscle and brain. All tissues reflected differences in T-Hg accumulation in both species, although D. labrax accumulated higher levels. Regarding MT, D. labrax revealed a depletion in brain MT content and an incapacity to induce MT synthesis in all the other tissues, whereas L. aurata showed the ability to increase MT in liver and muscle. Tissue-specificities were exhibited in the MT inducing potential and in the susceptibility to MT decrease. L. aurata results presented muscle as the most responsive tissue. None of the investigated tissues displayed significant correlations between T-Hg and MT levels. Overall, the applicability of MT content in fish tissues as biomarker of exposure to mercury was uncertain, reporting limitations in reflecting the metal exposure levels and the subsequent accumulation extent.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.     

围场县农田典型药物和个人护理品污染特征与生态风险预评价

利用超声萃取-固相萃取-高效液相色谱/串联质谱(LC-MS/MS)技术,对围场县全县农田中5个大类(磺胺类、四环素类、氟喹诺酮类、大环内酯类以及其他类)25种典型药物和个人护理品(PPCPs)的污染水平进行了调查,并采用风险熵法对其进行生态风险预评价。结果表明:有23种目标PPCPs被检出,不同目标物检出率差异显著,检出含量范围为0.38~6.50μg·kg-1,单种污染物最高检出浓度为101.9μg·kg-1(磺胺甲恶唑)。以目标物划分,分别有7种和5种被检出物质达到生态高风险和中等风险水平;以采样区域划分,41个土壤点位中分别有17个和12个达到生态高风险和中等风险水平。畜用PPCPs是围场农田中PPCPs污染物的主要来源,兽药滥用、粪便自然堆沤等传统农耕模式有造成农田土壤中PPCPs累积的趋势,因此需严控PPCPs污染源头,并推进畜禽粪便安全的资源化利用,以减缓农田土壤中由于PPCPs污染带来的潜在生态风险,保障围场地区生态环境功能、农田环境质量以及农产品安全品质。     

长三角地区池塘养殖水产品体内农药类污染与食用风险评价

为了解池塘养殖水产品体内的农药污染情况,以便为水产品质量评价及保障当地居民的饮食健康提供科学依据,本研究采用气相色谱质谱联用法(GC-MS)对长三角地区13个养殖池塘中5类(蟹类、鳖类、蚌类、虾类、鱼类)水产品体内9种有机磷农药(OPPs)、8种有机氯农药(OCPs)以及4种拟除虫菊酯类农药(SPs)进行了检测,并初步分析了其污染来源。结果表明,水产品体内3类农药均有检出,但残留水平均不高,OPPs残留总量为未检出至299 ng·g-1(dw),三唑磷、伏杀硫磷、喹硫磷和毒死蜱较易在水产品体内蓄积;OCPs残留总量为16~82 ng·g-1(dw),主要污染物为六六六(HCHs),主要来自历史残留;SPs残留总量为44~89 ng·g-1(dw),主要污染物为高效氯氟氰菊酯。水产品体内的农药污染可能与养殖池塘中的沉积物污染密切相关。5类水产品体内3类农药的总风险指数(HI)为0.0020~0.046,远小于1,因此,长三角地区由3类农药造成的健康风险处于安全水平。     

生活生产类产品VOCs含量限值法规与标准研究

本文对国内生活生产类产品VOCs含量限值的国家标准、地方标准、行业标准以及中国香港、欧美等发达地区精细化的生活生产类产品VOCs含量限值法规和标准做了比较全面的综述,并从产品限值种类以及限值要求两个方面进行了对比研究和分析,提出了我国生产生活类产品VOCs 含量限值法规标准制定建议。笔者认为,应借鉴发达国家成功的生活生产类产品VOCs含量限值法规及标准制定经验,从做好标准和产品技术要求衔接、建立区域协同制定标准模式、结合经济因素或环境空气质量,分步推进相关标准制定和发布等方面入手,建立符合实际国情的产品种类较为全面、标准要求较高的生产生活类产品VOCs含量限值法规与标准体系,尤其是生活消费品方面,减少直接与人体接触的生活消费品VOCs排放。