Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.     

Assessing the spatial distribution of grassland age in a marginal European landscape

Grassland age is increasingly recognised to be an indicator for present-day biodiversity, e.g. plant species richness, and is also important for other landscape functions. We developed a methodological approach to systematically assess the spatial distribution of grassland age in marginal European landscapes. This approach - applied to the Lahn-Dill Highlands (1270 km(2)), a marginal landscape in Hesse, Germany - comprises three steps: (1) in a two-stage stratification process, we pre-stratified the study area according to recent land-cover patterns and their changes between 1955 and 1995 (stratification I) and classified grassland types by combining data on soil moisture, base-richness, and elevation (stratification II). From 50 grassland types, we randomly selected 1000 representative grassland patches. (2) We determined the age of these patches by means of aerial photograph interpretation of a chronosequence dating back to 1953 and classified each patch with respect to the age classes young (<18 years), mid-aged (18-47 years), and old (>47 years). (3) Based on this information, we calculated grassland type-specific probabilities for grassland patches to belong to the respective age classes. These probabilities were projected to districts by direct extrapolation. An exemplary validation of extrapolation results for two test areas was performed. The results revealed that 49% of the investigated patches were old grassland. The remaining patches were mid-aged (36%) or young grassland (15%). The extrapolation results indicated accordingly a predominance of old grassland at the district scale. Occurrences of mid-aged grassland were concentrated in districts with a pronounced land-cover change, whereas young grassland is apparently evenly distributed across the study area. Validation results suggest that our approach is suitable for a realistic estimation of grassland age in marginal European landscapes. The method may be applied in landscape models of various disciplines that rely on large-scale information on grassland age.     

Bestimmung von Mineralölkohlenwasserstoffen in Bodenproben mit Hilfe der Dünnschichtchromatographie

A thin-layer chromatographic method for the determination of mineral oil hydrocarbons (aliphatic compounds and naphtenes) of medium and low volatility in soil samples is presented which is based on their separation and quantitative determination. The extraction of the soil samples is effected by means of an n-hexane-acetone mixture (10∶1) supported by ultrasonics. The evaluation can be made visually or densitometrically by means of a thin-layer scanner. The applicability and restrictions of the method are shown. The advantage of the method lies in its low requirements pertaining to apparatus and chemicals, as well as in its rapidness which makes it suitable for quick in-situ analyses as, for example, for the assessment of the mineral oil content of a contaminated site.     

Climate change stimulates the growth of the intertidal macroalgae <Emphasis Type="Italic">Ascophyllum nodosum</Emphasis> near the northern distribution limit

Ascophyllum nodosum is a foundation macroalgae of the intertidal zone that distributes across latitude 41.3–69.7°N. We tested the hypothesis that growth of A. nodosum near the northern distribution edge increases with warming. We retrospectively quantified the growth of eight A. nodosum populations at West Greenland and North Norway (from 64°N to 69°N). For seven populations, we measured growth rates since 1997–2002 and for one of them we extended the time series back to 1956 using published estimates. Individuals at northern populations elongated between 2.0 and 9.1 cm year^?1 and this variability correlated with temperature and annual ice-free days. A spatial comparison of A. nodosum growth across the species distribution range showed that Northern (and coldest) populations grew at the slowest rates. Our results demonstrate that arctic climate change enhances the growth of A. nodosum populations and suggest that their productivity may increase in response to projected global warming.     

Geoelectrical methods for monitoring geological CO2 storage: First results from cross-hole and surface–downhole measurements from the CO2SINK test site at Ketzin (Germany)

The feasibility of monitoring CO₂ migration in a saline aquifer at a depth of about 650 m with cross-hole and surface–downhole electrical resistivity tomography (ERT) is investigated at the CO₂SINK test site close to Ketzin (Germany). The permanent vertical electrical resistivity array (VERA) consists of 45 electrodes (15 in the injection well Ktzi201 and 15 in each of the two observation wells Ktzi200 and Ktzi202), successfully placed on the electrically insulated casings, in the depth range of about 590–740 m with a spacing of about 10 m. The three Ketzin wells are arranged as perpendicular triangle with distances of 50 and 100 m.First synthetic modelling studies indicate an increase of the electrical resistivity of about 200% caused by CO₂ injection, corresponding to a bulk CO₂ saturation of 50%, which is in good agreement with laboratory studies. Finite difference inversion of field data delivers three-dimensional resistivity distributions between the wells which are consistent with the reservoir modelling studies.To increase the limited observation area provided by the cross-hole measurements, additional surface–downhole measurements were deployed. A main CO₂ migration in SE–NW direction is deduced from surface to downhole resistivity experiments.The first cross-hole time-lapse results show that the resolution and the coverage of the electrode array in the Ketzin setting are sufficient to resolve the expected resistivity changes on the characteristic length scale of the electrode array. Significant resistivity changes could be measured, however, detailed information on the CO₂ plume could not be resolved yet by VERA under the existing geological circumstances.     

Persistent halogenated organic contaminants and mercury in northern fulmars (Fulmarus glacialis) from the Canadian Arctic

Northern fulmars from two breeding colonies in the Canadian Arctic, Cape Vera and Prince Leopold Island, were analyzed for organochlorine pesticides, PCBs, perfluorinated compounds (PFCs) and total mercury (Hg). Hepatic concentrations of organochlorines and Hg were highest in the male fulmars from Cape Vera. Perfluorooctane sulfonate (PFOS) concentrations did not vary significantly between sexes or colonies. However, concentrations of the perfluorinated carboxylates (PFCAs) were higher in fulmars from Cape Vera than Prince Leopold Island. The C₁₁-C₁₅ PFCAs averaged 90% of the PFCA profile at both colonies. Polychorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs (NO-PCBs) were measured only in birds from Prince Leopold Island. Concentrations of PCDDs, PCDFs, NO-PCBs and Toxic Equivalents (TEQs) did not differ significantly between sexes. ΣTEQ was comprised mainly of ΣTEQ_PCDF. Concentrations of Hg and the persistent halogenated compounds reported in this study were below published toxicological threshold values for wild birds.     

北京夏季高温高湿和降水过程对大气颗粒物谱分布的影响

2004-07-13～2004-08-23使用TDMPS-APS系统在线测量颗粒物的数浓度谱分布,并于07-16～07-18选取了高温闷热夜晚、日间高温高湿和雨后晴朗干洁3种天气条件,使用多级串联撞击式采样器(MOUDI)测量颗粒物的质量浓度谱分布,结果表明,高温高湿天气条件下颗粒物的污染、尤其细粒子污染严重,导致很低的能见度(2.5km);PM_1.8和PM₁₀的质量浓度分别为170.68μg/m³和249.35μg/m³,细粒子质量浓度占PM10的68%;粒径为50～100nm颗粒物的数浓度最高,为2×10⁴～3×10⁴个/cm³;降雨过程对粗粒子和细粒子均有去除作用,对细粒子的去除作用尤为明显;降雨后PM₁₀和PM_1.8浓度分别比降雨前降低3倍和6倍;降雨过后的晴朗干洁天气有利于新粒子(3～20nm)的生成,生成的新粒子快速长大到50～100nm;随着污染物的累积,以后几天内又变为污染天气.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

Biocatalytic dechlorination of lindane by nano-scale particles of Pd(0) deposited on Shewanella oneidensis

A new approach for the removal of the pesticide lindane (gamma-hexachlorocyclohexane or gamma-HCH) makes use of catalytic reduction of HCH to benzene over a metal catalyst, namely Pd(0). Since specific surface area plays an important role in reactivity of catalysts, this study investigated the use of bioPd(0), i.e. nano-scale Pd(0) particles precipitated on the biomass of Shewanella oneidensis, for the removal of lindane. It was demonstrated that bioPd(0) has catalytic activity towards dechlorination of gamma-HCH, with the addition of formate as electron donor, and that dechlorination with bioPd(0) was more efficient than with commercial powdered Pd(0). The biodegradable compound benzene was formed as reaction product and other HCH isomers could also be dechlorinated. Subsequently bioPd(0) was implemented in a membrane reactor technology for the treatment of gamma-HCH polluted water. In a fed-batch process configuration with formate as electron donor, a removal percentage of 98% of gamma-HCH saturated water (10 mg l(-1)) was achieved within 24h. The measured chloride mass balance approached the theoretical value. The results of this work showed that a complete, efficient and fast removal of lindane was achieved by biocatalysis with bioPd(0).     

Temporal trends of organochlorines and mercury in seabird eggs from the Canadian Arctic, 1975-2003

Organochlorine pesticides, PCBs, total mercury and selenium were measured in eggs of thick-billed murres, northern fulmars and black-legged kittiwakes collected from Prince Leopold Island in the Canadian High Arctic between 1975 and 2003. The primary organochlorines found were SigmaPCB, p,p'-DDE, oxychlordane, and hexachlorobenzene (HCB). Most of organochlorines analyzed showed either significant declines or no significant change between 1975 and 2003 in all three species. However, significant increases were observed for SigmaHCH in the kittiwakes and fulmars, and beta-HCH in the murres and fulmars. Mercury increased significantly in eggs of murres and fulmars, whereas mercury in the kittiwakes did not change significantly over the study period. Statistical analyses included stable-nitrogen isotope ratios (delta(15)N) to control for any variation in trophic level over time. Although the contaminant concentrations reported in this study are below published threshold values, mercury and beta-HCH concentrations continue to increase suggesting that continued monitoring is warranted.