Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.     

Evaluation of food chain transfer of the antibiotic oxytetracycline and human risk assessment

There has been recent concern regarding the possibility of antibiotics entering the aquatic food chain and impacting human consumers. This work reports experimental results of the bioconcentration of the antibiotic oxytetracycline (OTC) by the Asian watermeal plant (Wolffia globosa Hartog & Plas) and bioaccumulation of OTC in watermeal and water by the seven-striped carp (Probarbus jullieni). They show, for the first time, the extent to which OTC is able to transfer from water to plant to fish and enter the food chain. The mean bioconcentration factor (dry weight basis) with watermeal was 1.28 × 10³ L kg⁻¹. Separate experiments were undertaken to characterize accumulation of OTC by carp from water and watermeal. These showed the latter pathway to be dominant under the conditions employed. The bioconcentration and biomagnification factors for these processes were 1.75 L kg⁻¹ and 2 × 10⁻⁴ kg g⁻¹ respectively. Using an aqueous concentration range of 0.34–3.0 μg L⁻¹, hazard quotients for human consumption of contaminated fish of 1.3 × 10⁻² to 1.15 × 10⁻¹ were derived.     

Reducing phosphorus flux from organic soils in surface flow treatment wetlands

Treatment wetlands have a finite period of effective nutrient removal after which treatment efficiency declines. This is due to the accumulation of organic matter which decreases the capacity and hydraulic retention time of the wetland. We investigated four potential solutions to improve the soluble reactive P (SRP) removal of a municipal wastewater treatment wetland soil including; dry down, surface additions of alum or calcium carbonate and physical removal of the accreted organic soil under both aerobic and anaerobic water column conditions. The flux of SRP from the soil to the water column under aerobic conditions was higher for the continuously flooded controls (1.1 ± 0.4 mg P m⁻² d⁻¹), dry down (1.5 ± 0.9 mg P m⁻² d⁻¹) and CaCO₃ (0.8 ± 0.7 mg P m⁻² d⁻¹) treatments while the soil removal and alum treatments were significantly lower at 0.02 ± 0.10 and −0.07 ± 0.02 mg P m⁻² d⁻¹, respectively. These results demonstrate that the two most effective management strategies at sequestering SRP were organic soil removal and alum additions. There are difficulties and costs associated with removal and disposal of soils from a treatment wetland. Therefore our findings suggest that alum addition may be the most cost effective and efficient means of increasing the sequestering of P in aging treatment wetlands experiencing reduced P removal rates. However, more research is needed to determine the longer term effects of alum buildup in the organic soil on the wetland biota, in particular, on the macrophytes and invertebrates. Since alum effectiveness is time limited, a longer term solution to P flux may favor the organic soil removal.     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

Effect of Ca2+-ions on the absorption of Pb2+, Cu2+, Cd2+ and Zn2+ by humic substances

Distribution coefficients for the sorption of Pb²⁺, Cu²⁺, Cd²⁺ and Zn²⁺ by peat were determined as a function of the Ca²⁺-content of peat as well as of the Ca²⁺-concentration in the solution. The amount of heavy metal ions taken up was measured for Cu²⁺, Cd²⁺ and Zn²⁺ by atomic absorption spectrometry and for Pb²⁺ by using Pb-212 as a radioactive tracer.The results show that the distribution coefficients of the heavy metal ions increase, if one increases the initial ratio of the $\text{Ca}{}^{\mathrm{2+}}\text{H}{}^{\mathrm{+}}\text{-}\text{ions}$ in the peat phase. The distribution coefficients for the heavy metal ions decrease, however, if - at constant initial Ca²⁺-content of the peat - the Ca²⁺-concentration of the solution is increased.     

Assessment of nitrogen losses through nitrous oxide from abattoir wastewater-irrigated soils

The land disposal of waste and wastewater is a major source of N₂O emission. This is due to the presence of high concentrations of nitrogen (N) and carbon in the waste. Abattoir wastewater contains 186 mg/L of N and 30.4 mg/L of P. The equivalent of 3 kg of abattoir wastewater-irrigated soil was sieved and taken in a 4-L plastic container. Abattoir wastewater was used for irrigating the plants at the rates of 50 and 100 % field capacity (FC). Four crop species were used with no crop serving as a control. Nitrous oxide emission was monitored using a closed chamber technique. The chamber was placed inside the plastic container, and N₂O emission was measured for 7 days after the planting. A syringe and pre-evacuated vial were used for collecting the gas samples; a fresh and clean syringe was used each time to avoid cross-contamination. The collected gas samples were injected into a gas chromatography device immediately after each sampling to analyse the concentration of N₂O from different treatments. The overall N₂O emission was compared for all the crops under two different abattoir wastewater treatment rates (50 and 100 % FC). Under 100 % FC (wastewater irrigation), among the four species grown in the abattoir wastewater-irrigated soil, Medicago sativa (23 mg/pot), Sinapis alba (21 mg/pot), Zea mays (20 mg/pot) and Helianthus annuus (20 mg/pot) showed higher N₂O emission compared to the 50 % treatments—M. sativa (17 mg/pot), S. alba (17 mg/pot), Z. mays (18 mg/pot) and H. annuus (18 mg/pot). Similarly, pots with plants have shown 15 % less emission than the pots without plants. Similar trends of N₂O emission flux were observed between the irrigation period (4-week period) for 50 % FC and 100 % FC. Under the 100 % FC loading rate treatments, the highest N₂O emission was in the following order: week 1 > week 4 > week 3 > week 2. On the other hand, under the 50 % FC loading rate treatments, the highest N₂O emission was recorded in the first few weeks and in the following order: week 1 > week 2 > week 3 > week > 4. Since N₂O is a greenhouse gas with high global warming potential, its emission from wastewater irrigation is likely to impact global climate change. Therefore, it is important to examine the effects of abattoir wastewater irrigation on soil for N₂O emission potential.

     

Phosphine in paddy fields and the effects of environmental factors

Ambient levels of phosphine (PH₃) in the air, phosphine emission fluxes from paddy fields and rice plants, and the distribution of matrix-bound phosphine (MBP) in paddy soils were investigated throughout the growing stages of rice. The relationships between MBP and environmental factors were analyzed to identify the principal factors determining the distribution of MBP. The phosphine ambient levels ranged from 2.368 ± 0.6060 ng m⁻³ to 24.83 ± 6.529 ng m⁻³ and averaged 14.25 ± 4.547 ng m⁻³. The highest phosphine emission flux was 22.54 ± 3.897 ng (m² h)⁻¹, the lowest flux was 7.64 ± 4.83 ng (m² h)⁻¹, and the average flux was 14.17 ± 4.977 ng (m² h)⁻¹. Rice plants transport a significant portion of the phosphine emitted from the paddy fields. The highest contribution rate of rice plants to the phosphine emission fluxes reached 73.73% and the average contribution was 43.00%. The average MBP content of 111.6 ng kg⁻¹fluctuated significantly in different stages of rice growth and initially increased then decreased with increasing depth. The peak MBP content in each growth stage occurred approximately 10 cm under the surface of paddy soils. Pearson correlation analyses and stepwise multiple regression analysis showed that soil temperature (Ts), acid phosphatase (ACP) and total phosphorus (TP) were the principal environmental factors, with correlative rankings of Ts > ACP > TP.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

黄菖蒲和狭叶香蒲根系对氮磷的吸收动力学

采用改进的常规耗竭法,研究了黄菖蒲（Iris pseudacorus L.）和狭叶香蒲（Typha angustifolia L.）根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收特征及差异。结果表明,这2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收动力学特征均可采用Michaelis-Menten方程描述。2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的亲和力（Km）和最大吸收速率（Vmax）有显著差异。吸收H₂PO₄^-时,黄菖蒲根系具有较高的Vmax值和较低的Km值,说明黄菖蒲具有嗜磷特性,并能够适应广范围浓度的H₂PO₄^-环境,适宜用于污染水体磷的去除;吸收NO₃^-时,狭叶香蒲根系具有较高的Vmax值和较低的Km值,表明狭叶香蒲可用于广范围浓度NO₃^-污染的水体修复;吸收NH₄⁺时,黄菖蒲根系具有较低的Vmax值和Km值,而狭叶香蒲根系具有较高的Vmax值和Km值,说明黄菖蒲适宜用于NH₄⁺污染较轻水体的修复,而在NH₄⁺污染较重水体中宜选用狭叶香蒲作为先锋植物。     

Fungi and bacteria in mould-damaged and non-damaged office environments in a subarctic climate

The fungi and bacterial levels of the indoor air environments of 77 office buildings were measured in winter and a comparison was made between the buildings with microbe sources in their structures and those without such sources. Penicillium, yeasts, Cladosporium and non-sporing isolates were the commonest fungi detected in the indoor air and in settled dust, in both the mould-damaged and control buildings. Aspergillus ochraceus, Aspergillus glaucus and Stachybotrys chartarium were found only in environmental samples from the mould-damaged buildings. Some other fungi, with growth requiring of water activity, a_w, above 0.85, occurred in both the reference and mould-damaged buildings, but such fungi were commoner in the latter type of buildings. The airborne concentrations of Penicillium, Aspergillus versicolor and yeasts were the best indicators of mould damage in the buildings studied. Penicillium species and A. versicolor were also the most abundant fungi in the material samples. This study showed that the fungi concentrations were very low (2–45 cfu m⁻³ 90% of the concentrations being <15 cfu m⁻³) in the indoor air of the normal office buildings. Although the concentration range of airborne fungi was wider for the mould-damaged buildings (2–2470 cfu m⁻³), only about 20% of the samples exceeded 100 cfu m⁻³. The concentrations of airborne bacteria ranged from 12 to 540 cfu m⁻³ in the control buildings and from 14 to 1550 cfu m⁻³ in the mould-damaged buildings. A statistical analysis of the results indicated that bacteria levels are generally <600 cfu m⁻³ in office buildings in winter and fungi levels are <50 cfu m⁻³. These normal levels are applicable to subarctic climates for urban, modern office buildings when measurements are made using a six-stage impactor. These levels should not be used in evaluations of health risks, but elevated levels may indicate the presence of abnormal microbe sources in indoor air and a need for additional environmental investigations.     

Aerosol indirect effect over Indo-Gangetic plain

Moderate resolution imaging spectroradiometer (MODIS) data are analyzed over the Indo-Gangetic plain (IGP) to study the effect of aerosol optical depth (AOD) on the water (R_eff,w) and ice (R_eff,i) cloud effective radius for the period 2001–2005. The temporal variation of R_eff,w and R_eff,i shows reverse trend as that of AOD for most of the time. The intensity of positive indirect effect (i.e. increase of R_eff,w/i with decrease of AOD and vice versa) is the highest in winter (ΔR_eff,w/ΔAOD∼−9.67 μm and ΔR_eff,i/ΔAOD∼−12.15 μm), when the role of meteorology is the least. The positive indirect effect is significant in 43%, 37%, 68% and 54% of area for water clouds in winter, pre-monsoon, monsoon and post-monsoon seasons, respectively, whereas the corresponding values for ice clouds are 42%, 35%, 53% and 53% for the four seasons, respectively. On the contrast, R_eff,i in some locations shows increment with the increase in AOD (negative indirect effect). The negative indirect effect is significant at 95% confidence level in 7%, 18%, 9% and 6% grids for winter, pre-monsoon, monsoon and post-monsoon seasons, respectively. The restricted spatial distribution of negative indirect effect in IGP shows that the cloud microphysical processes are very complex. Our analyses clearly identify the contrasting indirect effect, which requires further in situ investigations for better understanding of the aerosol–cloud interaction in the region.     

Long-term variation of PM2.5 levels and composition at rural, urban, and roadside sites in Hong Kong: Increasing impact of regional air pollution

Long-term study of air pollution plays a decisive role in formulating and refining pollution control strategies. In this study, two 12-month measurements of PM_2.5 mass and speciation were conducted in 00/01 and 04/05 to determine long-term trend and spatial variations of PM_2.5 mass and chemical composition in Hong Kong. This study covered three sites with different land-use characteristics, namely roadside, urban, and rural environments. The highest annual average PM_2.5 concentration was observed at the roadside site (58.0±2.0 μg m⁻³ (average±2σ) in 00/01 and 53.0±2.7 μg m⁻³ in 04/05), followed by the urban site (33.9±2.5 μg m⁻³ in 00/01 and 39.0±2.0 μg m⁻³ in 04/05), and the rural site (23.7±1.9 μg m⁻³ in 00/01 and 28.4±2.4 μg m⁻³ in 04/05). The lowest PM_2.5 level measured at the rural site was still higher than the United States’ annual average National Ambient Air Quality Standard of 15 μg m⁻³. As expected, seasonal variations of PM_2.5 mass concentration at the three sites were similar: higher in autumn/winter and lower in summer. Comparing PM_2.5 data in 04/05 with those collected in 00/01, a reduction in PM_2.5 mass concentration at the roadside (8.7%) but an increase at the urban (15%) and rural (20%) sites were observed. The reduction of PM_2.5 at the roadside was attributed to the decrease of carbonaceous aerosols (organic carbon and elemental carbon) (>30%), indicating the effective control of motor vehicle emissions over the period. On the other hand, the sulfate concentration at the three sites was consistent regardless of different land-use characteristics in both studies. The lack of spatial variation of sulfate concentrations in PM_2.5 implied its origin of regional contribution. Moreover, over 36% growth in sulfate concentration was found from 00/01 to 04/05, suggesting a significant increase in regional sulfate pollution over the years. More quantitative techniques such as receptor models and chemical transport models are required to assess the temporal variations of source contributions to ambient PM_2.5 mass and chemical speciation in Hong Kong.     

Accumulation and quantitative estimates of airborne lead for a wild plant (Aster subulatus)

Foliar uptake of airborne lead is one of the pathways for Pb accumulation in plant organs. However, the approximate contributions of airborne Pb to plant organs are still unclear. In the present study, aerosols (nine-stage size-segregated aerosols and total suspended particulates), a wild plant species (Aster subulatus) and the corresponding soils were collected and Pb contents and isotopic ratios in these samples were analyzed. Average concentration of Pb was 96.5 ± 63.5 ng m⁻³ in total suspended particulates (TSP) and 20.4 ± 5.5 ng m⁻³ in the fine fractions of size-segregated aerosols (SSA) (<2.1 μm), higher than that in the coarser fractions (>2.1 μm) (6.38 ± 3.71 ng m⁻³). Enrichment factors show that aerosols and soils suffered from anthropogenic inputs and the fine fractions of the size-segregated aerosols enriched more Pb than the coarse fractions. The order of Pb contents in A. subulatus was roots > leaves > stems. The linear relationship of Pb isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) among soil, plant and aerosol samples were found. Based on the simple binary Pb isotopic model using the mean ²⁰⁶Pb/²⁰⁷Pb ratios in TSP and in SSA, the approximate contributions of airborne Pb into plant leaves were 72.2% and 65.1%, respectively, suggesting that airborne Pb is the most important source for the Pb accumulation in leaves. So the combination of Pb isotope tracing and the simple binary Pb isotope model can assess the contribution of airborne Pb into plant leaves and may be of interest for risk assessment of the exposure to airborne Pb contamination.     

Two extreme types of mixing of dust with urban aerosols observed in Kosa particles: ‘After’ mixing and ‘on-the-way’ mixing

Besides well-known episodic Kosa during spring, high concentrations of Ca²⁺ in aerosols were observed early in summer as well as in the semi-continuous data of the aerosols at the summit of Mt. Fuji. We further analysed the data to study the chemical characteristics of the high calcium event during early summer. The back trajectory analyses of the event indicated that Ca was transported from arid and semi-arid regions (e.g. the Taklamakan desert) through the westerly-dominated troposphere higher than the height of the summit of Fuji. The amount of SO₄^2? was always equivalent to that of NH₄⁺ unlike the case of the normal Kosa period where SO₄^2? is in excess with respect to NH₄⁺. This shows the ‘after’ mixing of unreacted CaCO₃ of Kosa origin with (NH₄)₂SO₄, which was only realized by the downward injection of Kosa particles from higher altitudes to the air masses of different origin. In the case of normal Kosa, the air bearing Kosa particles passed through the polluted area to absorb unneutralized acids (‘on-the-way’ mixing), whereas in the case of the Kosa-like phenomena in summer, the acids from the polluted area have been neutralized by NH₄⁺ and become inactive before mixing with CaCO₃ (“after” mixing). We have simplified the chemistry of aerosols using their three major components, Ca²⁺, SO₄^2? and NH₄⁺, and introduced a new triangle diagram with the three assumed end-members of CaCO₃, CaSO₄ and (NH₄)₂SO₄ to quantify the contribution of the ‘after’ mixing to the aerosols (AMI; ‘after’ mixing index). Based on the back trajectories of some high AMI cases, CaCO₃ in Kosa particles was transported through the middle troposphere (5000–7000 m) and descended to meet another air mass where SO₄^2? had been already neutralized by NH₃.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Sources of hydrogen peroxide in cloudwater

Results of a theoretical investigation of H₂O₂ formation in cloud droplets arising from gaseous HO₂ radical scavenging are presented. It is shown that this process is pH dependent with the maximum rate of H₂O₂ production occurring below pH 3. This dependence arises as a result of the dissociation of HO₂ in water (pK_a = 4.9) and the subsequent disproportionation reaction of HO₂ and O₂⁻ to form hydrogen peroxide. O₂⁻ is also removed by reaction with O₃ to produce OH radicals and this process becomes more competitive as both the pH and $\text{O}{}_2{}^{\mathrm{-}}\text{HO}{}_2$ ratio increase. The presence of soluble organic species, such as aldehydes, in cloudwater counteracts the effect of ozone by converting OH back to HO₂. For low pHs (< 3) the net contribution of organic solutes of H₂O₂ production is predicted to be relatively small, being limited by the availability of OH radicals scavenged from the gas phase. Existing cloud chemistry models may overestimate the rate of aqueous oxidation of formaldehyde by OH radicals.Under conditions where scavenging of gas-phase free radicals by cloud droplets is efficient, uptake of HO₂ radicals may be reversible. The aqueous concentration of OH is unlikely to approach thermodynamic equilibrium with the gas phase (H ∼-30 M atm⁻¹ and can be treated as irreversible. In clouds with a small mean droplet radius, efficient scavenging of precursor OH radicals should result in a decrease in gas-phase HO₂ production with a reduction in the yield of aqueous H₂O₂, although this is offset by the presence of soluble organic species. A similar effect is predicted for clouds with a high liquid water content.The supply of HO₂ and OH radicals to cloud droplets is controlled by gas-phase ozone chemistry which is in turn dependent on the solar u.v. radiation intensity. The u.v. density in clouds may be higher than in clear air when the solar zenith angle is small, thus enhancing H₂O₂ production, but falls off markedly as the solar zenith angle becomes larger. Predicted rates of H₂O₂ formation in clouds based on midday conditions are likely to be considerably higher than the average daytime value, particularly in summer. Diurnal and seasonal effects on H₂O₂ generation are expected to be more marked in clouds than in clear air.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.