Systematic comparison of ILWAS, MAGIC, and ETD watershed acidification models: 3. Mass balance budgets for acid neutralizing capacity

Three watershed acidification models-ILWAS, MAGIC, and ETD-were quantitatively compared to determine model structural differences by using a combination of input mapping and ANC mass balance budgets. Input mapping is a set of rules and algorithms to ensure that consistent input values were simultaneously derived for all three models. ANC budget analysis under current SO4(2-) deposition and a 70% reduction in SO4(2-) deposition allows examination of the relative importance of biogeochemical processes in affecting predictions of ANC or predicted changes in ANC. Model inputs were based on two dissimilar watersheds having characteristics typical of watersheds in the northeastern US. After mapping inputs, the three models predicted values of outflow ANC fluxes that were similar among the models for each watershed and deposition scenario. Within each watershed, the changes in outflow ANC fluxes between the scenarios were similar for the three models. Terrestrial weathering was the major source of ANC for all three models for both watersheds and deposition scenarios. The contributions of other processes to the ANC of the two watersheds were, under certain conditions, model-specific. Cation exchange was responsible for changes in ANC when deposition decreased for the three models. Other processes responsible for changes in ANC between scenarios were SO4(2-) sorption (for MAGIC) and in-lake weathering (for ETD). The processes responsible for the change in ANC from a change in deposition (cation exchange, SO4(2-) sorption, and in-lake weathering) were different from the processes contributing to the absolute ANC for a given deposition scenario (terrestrial weathering). The budget analysis complements an earlier Monte Carlo analysis that showed that the three models are structurally different and that predictions viewed on a relative scale are more similar than absolute scale predictions.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Modelling long-term cation supply in acidified forest stands

A dynamic soil chemistry model was used to explain the observed decrease in soil base saturation between 1949 and 1984 at three stands in southern Sweden. The results show that acid deposition has caused soil acidification. The model, SAFE (Soil Acidification in Forest Ecosystems), includes the fundamental physical processes such as leaching and accumulation, and chemical processes such as cation exchange, mineral weathering, nutrient uptake and solute equilibrium reactions. The sources and sinks of base cations in the soil system were quantified, showing that weathering, deposition of base cations and depletion of exchangeable base cations supply cations to the soil solution in similar amounts in the upper 1 m during the acidification phase. This demonstrates that budget studies alone cannot be used to distinguish between long-term capacity to resist acidification, represented by weathering, from short-term buffering caused by cation exchange.     

Adsorption of lambda-cyhalothrin and cypermethrin on two typical Chinese soils as affected by copper

Background, aim, and scope  Pesticides and heavy metals pollution in soil environment has become a serious problem in many countries including China. Repeated applications of bordeaux mixture (a blend of copper sulfate and calcium hydroxide) and pyrethroid (Pys) insecticides have led to elevated copper (Cu) and Pys concentrations in vineyard surface soils. However, few studies focused on the interaction of Pys and heavy metals in the soil environment. Our previous studies had indicated the combined effect of cypermethrin (CPM) and Cu on soil catalase activity. Also, we had suggested that the addition of Cu could catalyze photo-degradation of CPM and lambda-cyhalothrin (λ-CHT) in aqueous solution and restrain their degradation in soil. To better understand the potential influence of Cu on the fate of Pys in the soil environment, the aim of the present work was to examine the effect of Cu on the adsorption of λ-CHT and CPM on two typical Chinese soils with different soil characteristics, which was one of the key processes controlling the fate of Pys, and to provide more information about the potential ecological risk of chemicals on the soil ecosystem. Fourier transform infrared and point charges analysis using the MOPAC program of the Gaussian system were also used to reveal the probable adsorption mechanism of λ-CHT and CPM on soils. Materials and methods  Two vineyard soils with different properties were chosen as experimental samples. They were sampled from 0 to 10 cm, dried, and sieved to 2 mm. Each soil was spiked with copper sulfate solution to obtain the following total soil Cu concentrations: 100, 200, 400, 800, and 1,600 mg·kg⁻¹. The treated soils were incubated for 2 weeks and then dried at 20°C. For each soil sample and at each soil Cu concentration, the adsorption of λ-CHT and CPM was measured using a batch equilibrium method. The concentration of λ-CHT was determined by HPLC, and the amount of λ-CHT and CPM adsorbed by the soil sample at equilibrium was determined by the difference between the initial and equilibrium concentrations in solution corrected by the blank adsorption measurement. Results  Without the addition of Cu, the adsorption of λ-CHT and CPM on Black soil is greater than that on Red soil, while the adsorption of λ-CHT on both soils is significantly stronger than that of CPM. As the soil Cu concentration increased from 19 (or 18; background) to 1,600 mg·kg⁻¹, the adsorption coefficient (K _d) of λ-CHT decreased from 12.2 to 5.9 L·kg⁻¹ for Red soil, and from 26.1 to 16.8 L·kg⁻¹ for Black soil, whereas the CPM adsorption coefficient in both soils decreased nearly by 100% (K _d decreased from 9.4 to 0.2 L·kg⁻¹ for Red soil and from 16.2 to 0.5 L·kg⁻¹ for Black soil). Discussion  Pys adsorption is a surface phenomenon which depends on the surface area and the organic matter content. Thus, the Black soil, having higher organic matter and greater surface area than that of the Red soil, show greater adsorption affinity to λ-CHT and CPM. In our study, the different adsorption affinity of the two Pys was obtained, which was probably attributed to differences with respect to their physical–chemical properties. Further comparison upon the two Pys was conducted. The point charges of halogen atoms in the λ-CHT and CPM were calculated, the differences of which probably lead to the fact that λ-CHT has a stronger binding capacity to soils than CPM. Also, FTIR spectra show that competitive adsorption occurs between CPM and Cu for the same adsorption sites, which is responsible for the obtained suppression of CPM adsorption affected by Cu. Conclusions  Lambda-cyhalothrin shows a significantly stronger adsorption than cypermethrin on both soils. This phenomenon may be due to several reasons: (1) λ-CHT has lower solubility and a higher octanol–water partition coefficient value than CPM; (2) λ-CHT consists of specific isomers, whereas CPM is mixtures of eight different isomers; (3) the chlorine and fluorine atoms in the λ-CHT have a negative point charge, whereas the chlorine atoms in the CPM have a positive point charge. As the soil Cu concentrations increased from 19 (or 18) mg·kg⁻¹ to 1,600 mg·kg⁻¹, the adsorption coefficient of λ-CHT and CPM decreased on both soils. This is mainly due to a competition between Cu and Pys for occupying the adsorption sites on soils. The information from this study have important implications for vineyard and orchard soils, which often contain elevated levels of Cu and Pys. These results are also useful in assessing the environmental fate and health effect of λ-CHT and CPM. Recommendations and perspectives  It is important for environmental scientists and engineers to get a better understanding of soil–metal–organic contaminant interactions. However, pesticide adsorption involves complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behavior of pesticide. Therefore, considerable research should be carried out to understand the mechanism of interaction between Pys and heavy metal on soils clearly.     

Fenton-like oxidation and mineralization of phenol using synthetic Fe(II)–Fe(III) green rusts

Background, aim, and scope  

In literature, the environmental applications of green rust (GR) have mainly been pointed out through the reduction of inorganic contaminants and the reductive dechlorination of chlorinated organics. However, reactions involving GR for the oxidation and mineralization of organic pollutants remain very scantly described. In this study, the ability of three synthetic Fe(II)–Fe(III) green rusts, GR(CO₃²⁻), GR(SO₄²⁻), and GR(Cl⁻), to promote Fenton-like reaction was examined by employing phenol as a model pollutant. Unlike the traditional Fenton’s reagent (dissolved Fe(II) + H₂O₂), where the pH values have to be lowered to less than 4, the proposed reaction can effectively oxidize the organic molecules at neutral pH and could avoid the initial acidification which may be costly and destructive for the in situ remediation of contaminated groundwater and soils. The green rust reactivity towards the oxidative transformation of phenol was thoroughly evaluated by performing a large kinetic study, chemical analyses, and spectroscopic investigations.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Comparison of black carbon (BC) aerosols in two urban areas – concentrations and size distributions

In this study, the BC aerosol measured at two very different urban sites is compared in terms of concentration, seasonal variation, and size distribution. During a 14 month study, one impactor sample was performed each month on a day with typical meteorological conditions. One (Vienna) or three (Uji) filter samples were obtained during the sampling time of the impactors. BC concentration in both the filter and impactor samples was analyzed with an optical technique (integrating sphere technique), where a calibration curve obtained from commercial carbon black is used to convert the optical signal to BC mass. Gravimetric mass concentration was measured at both sites. The gravimetric mass size distribution was measured only in Vienna. At both sites, the yearly average of the BC concentration on the sampling days was around 5 μg m⁻³. In Vienna, some seasonal trend with high concentrations during the cold season was observed, while in Uji, no pronounced seasonal trend was found. The BC size distribution in Uji was distinctly bimodal in the submicron size range. Log-normal distributions were fitted through the impactor data. The average BC mass median diameters (MMD) of the two submicron modes were 0.15 and 0.39 μm. Each mode contained about the same amount of BC mass. In Vienna only one submicron BC mode (average MMD 0.3 μm) was found because of the low size resolution of the impactor. An analysis of humidity effects on the MMDs of BC (both sites) and gravimetric mass (Vienna only) indicates that the Vienna aerosol is partly mixed internally with respect to BC, while the Uji aerosol seems to be externally mixed.     

Historical record of black carbon in urban soils and its environmental implications

Energy use in urbanization has fundamentally changed the pattern and fluxes of carbon cycling, which has global and local environmental impacts. Here we have investigated organic carbon (OC) and black carbon (BC) in six soil profiles from two contrast zones in an ancient city (Nanjing) in China. BC in soils was widely variable, from 0.22 to 32.19 g kg⁻¹. Its average concentration in an ancient residential area (Zone 1) was, 0.91 g kg⁻¹, whereas in Zone 2, an industrial and commercial area, the figure was 8.62 g kg⁻¹. The ratio of BC/OC ranged from 0.06 to 1.29 in soil profiles, with an average of 0.29. The vertical distribution of BC in soil is suggested to reflect the history of BC formation from burning of biomass and/or fossil fuel. BC in the surface layer of soils was mainly from traffic emission (especially from diesel vehicles). In contrast, in cultural layers BC was formed from historical coal use. The contents of BC and the ratio of BC/OC may reflect different human activities and pollution sources in the contrasting urban zones. In addition, the significant correlation of heavy metals (Cu, Pb, and Zn) with BC contents in some culture layers suggests the sorption of the metals by BC or their coexistence resulted from the coal-involved smelting.     

Past and Present Permafrost Temperatures in the Abisko Area: Redrilling of Boreholes

Monitoring of permafrost has been ongoing since 1978 in the Abisko area, northernmost Sweden, when measurements of active layer thickness started. In 1980, boreholes were drilled in three mires in the area to record permafrost temperatures. Recordings were made twice per year, and the last data were obtained in 2002. During the International Polar Year (2007–2008), new boreholes were drilled within the ‘Back to the Future’ (BTF) and ‘Thermal State of Permafrost’ (TSP) projects that enabled year-round temperature monitoring. Mean annual ground temperatures (MAGT) in the mires are close to 0°C, ranging from −0.16 to −0.47°C at 5 m depth. Data from the boreholes show increasing ground temperatures in the upper and lower part by 0.4 to 1°C between 1980 and 2002. At one mire, permafrost thickness has decreased from 15 m in 1980 to ca. 9 m in 2009, with an accelerating thawing trend during the last decade.     

Contents and sources of DDT impurities in dicofol formulations in Turkey

Background, aim, and scope  Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods  Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p′ and o,p′ isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p′-Cl-DDT concentrations. Results  The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p′-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p′-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p’-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion  It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions  All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives  DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)     

A field survey—Staroe lake suffering from atmospheric deposition in the region north of the Arctic Circle

Background, aim, and scope  The Arctic holds large stores of minerals, and extracted materials are provided to the world’s economy; in this sense, the Arctic issue associated with mining is not local but global. In a part of the Arctic region (the Kola Peninsula, 66–70° N and 28–41° E), metal levels are generally elevated in the lake sediment. There is a question as to what results in elevated metal levels—a natural process (naturally abundant minerals) or an anthropogenic process (mining and metallurgy). In terms of solving this question, Staroe lake located on the Kola Peninsula was researched as a case study. Materials and methods  The following parameters were determined in relation with Staroe lake: (1) the current quality of the lake’s water—each 1,000-ml sample was collected at a surface point and a deep point (near the bottom layer), and the collected samples were directly analyzed after filtration; (2) atmospheric bulk deposition—bulk deposition was collected using a set of three rainwater samplers near the lake. In addition, bulk deposition was collected in a background site (250 km to the southwest of the smelter complex) as a reference; and (3) sediment profile (plus principal component analysis)—lake-bottom sediment was collected by an open-gravimetric column sampler equipped with an automatic diaphragm. After collection, the sample columns were cut at a 1-cm interval for analysis. Eigenvalues and variances by factor were calculated from the correlation coefficients. Results  The obtained data show that (1) naturally poor elements (Cu, Ni, Si, and SO₄ ²⁻) dominantly influence the lake’s water quality; (2) they are transported from the anthropogenic sources to the study lake through the atmospheric pathway; (3) mainly the contents of Cu, Ni, Sr, and Ca have influenced the sediment quality since the 1950s, corresponding to the industrial movement; and (4) Cu, Ni, and Sr originate from an anthropogenic source (smelter), and Ca originates from both natural and anthropogenic sources. Discussion  As compared with the Russian standard (San Pin 2.1.980–00), the contents of NO₃ ⁻ (50.3 ± 0.1 mg l⁻¹) and particulates (2.3 ± 0.2 mg l⁻¹) exceeded the standard levels (0.7 mg l⁻¹ NO₃ ⁻ and 45 mg l⁻¹ particulates); Staroe lake may be slightly contaminated. However, the contamination factor (comparison with the background data) implies that Staroe lake is considerably contaminated. There is a strong possibility that fine overburden detritus (<0.1 mm diameter) may be transported from an open pit to the study lake by natural forces such as wind. Although it is difficult to suppose that one factor dominantly affects the sediment quality, it follows from a factor analysis that factors 1 and 2 account for about 70% of the total variance: Factor 1 is the most dominant, and factor 2 is the second most dominant in the variability of sediment quality. It is considered that Cu, Sr, and Ni in factor 1 originate from anthropogenic sources because they are poor in sediment rocks. Conclusions  The field survey conducted in Staroe lake can give the following answers to the key objectives: (1) The present water quality is affected by Cu, Ni, Si, and SO₄ ²⁻ in light of the contamination factor, and these elements originate from anthropogenic sources (the smelter and the open pit) and are transported to the lake through the atmospheric pathway; (2) the sediment profile and statistic analysis show that the lake quality has been influenced by deposition of metals since the 1950s; and (3) Cu, Ni, Sr, and Ca have influenced the sediment quality in light of the most dominant factor—Cu, Ni, and Sr originate from an anthropogenic source, whereas Ca comes from both natural and anthropogenic sources. Recommendations and perspectives  The presented lake survey shows that the dispersion of human-related pollutants via the atmospheric pathway takes place in the Arctic region. If the current pollution continues without countermeasures, the high-latitude environment may lose its original characteristics; hence, this subject is important when considering how to implement a wide range of environmental protection measures in the Arctic.     

Simulating Dissolved Organic Carbon Dynamics at the Swedish Integrated Monitoring Sites with the Integrated Catchments Model for Carbon,INCA-C

Surface water concentrations of dissolved organic carbon ([DOC]) are changing throughout the northern hemisphere due to changes in climate, land use and acid deposition. However, the relative importance of these drivers is unclear. Here, we use the Integrated Catchments model for Carbon (INCA-C) to simulate long-term (1996–2008) streamwater [DOC] at the four Swedish integrated monitoring (IM) sites. These are unmanaged headwater catchments with old-growth forests and no major changes in land use. Daily, seasonal and long-term variations in streamwater [DOC] driven by runoff, seasonal temperature and atmospheric sulfate (SO₄ ²⁻) deposition were observed at all sites. Using INCA-C, it was possible to reproduce observed patterns of variability in streamwater [DOC] at the four IM sites. Runoff was found to be the main short-term control on [DOC]. Seasonal patterns in [DOC] were controlled primarily by soil temperature. Measured SO₄ ²⁻ deposition explained some of the long-term [DOC] variability at all sites.     

Recent Change in the Extent of Mangroves in the Northern Gulf of Papua,Papua New Guinea

Existing at the interface of land and sea, in regions of low topographic relief, mangroves are likely to be some of the first ecosystems that undergo spatial modification due to sea-level rise. The mangrove ecosystems of the Gulf of Papua New Guinea are some of the largest and most pristine in the Asia–Pacific region; they have not been subject to clearance for crustacean farming nor suffered from land reclamation projects. This article establishes through analysis of a time series of aerial photography and satellite imagery from the period 1973–2007, that there have been substantial changes in the distribution of mangroves in this region. These changes include the seaward progradation of the Purari Delta and the regression of the Kikori Delta by an average of 43 m year⁻¹ at its most seaward point. While these findings are likely to be continuations of long-term trends, it is probable that they can be explained by a variety of interacting factors including climate change, sea-level rise, subsistence in the northern Gulf of Papua and changes in sediment dynamics.     

Closing a Loop: Substance Flow Analysis of Nitrogen and Phosphorus in the Rainbow Trout Production and Domestic Consumption System in Finland

Ongoing eutrophication is changing the Baltic Sea ecosystem. Aquaculture causes relatively small-scale nutrient emissions, but local environmental impact may be considerable. We used substance flow analysis (SFA) to identify and quantify the most significant flows and stocks of nitrogen (N) and phosphorus (P) related to rainbow trout aquaculture in Finland. In 2004–2007, the input of nutrients to the system in the form of fish feed was 829 t N year⁻¹ and 115 t P year⁻¹. Around one-fifth of these nutrients ended up as food for human consumption. Of the primary input, 70% ended up in the Baltic Sea, directly from aquaculture and indirectly through waste management. The nutrient cycle could be closed partially by using local fish instead of imported fish in rainbow trout feed, thus reducing the net load of N and P to a fraction.     

Fractionation and mobility of phosphorus in a sandy forest soil amended with biosolids

Goal, Scope and Background Biosolids, i.e., treated sewage sludge, are commonly used as a fertilizer and amendment to improve soil productivity. Application of biosolids to meet the nitrogen (N) requirements of crops can lead to accumulation of phosphorus (P) in soils, which may result in P loss to water bodies. Since 1996, biosolids have been applied to a Pinus radiata D. Don plantation near Nelson City, New Zealand, in an N-deficient sandy soil. To investigate sustainability of the biosolids application programme, a long-term research trial was established in 1997, and biosolids were applied every three years, at three application rates, including control (no biosolids), standard and high treatments, based on total N loading. The objective of this study was to evaluate the effect of repeated application of biosolids on P mobility in the sandy soil. Materials and Methods Soil samples were collected in August 2004 from the trial site at depths of 0–10, 10–25, 25–50, 50–75, and 75–100 cm. The soil samples were analysed for total P (TP), plant-available P (Olsen P and Mehlich 3 P), and various P fractions (water-soluble, bioavailable, Fe and Al-bound, Ca-bound, and residual) using a sequential P fractionation procedure. Results and Discussion Soil TP and Olsen P in the high biosolids treatment (equivalent to 600 kg N ha⁻¹ applied every three years) had increased significantly (P<0.05) in both 0–10 cm and 10–25 cm layers. Mehlich 3 P in soil of the high treatment had increased significantly only at 0–10 cm. Olsen P appeared to be more sensitive than Mehlich 3 P as an indicator of P movement in a soil profile. Phosphorus fractionation revealed that inorganic P (Al/Fe-bound P and Ca-bound P) and residual P were the main P pools in soil, whereas water-soluble P accounted for approximately 70% of TP in biosolids. Little organic P was found in either the soil or biosolids. Concentrations of water-soluble P, bioavailable inorganic P (NaHCO₃ Pi) and potentially bioavailable inorganic P (NaOH Pi) in both 0–10 and 10–25 cm depths were significantly higher in the high biosolids treatment than in the control. Mass balance calculation indicated that most P applied with biosolids was retained by the top soil (0–25 cm). The standard biosolids treatment (equivalent to 300 kg N ha⁻¹ applied every three years) had no significant effect on concentrations of TP, Mehlich 3 P and Olsen P, and P fractions in soil. Conclusions The results indicate that the soil had the capacity to retain most biosolids-derived P, and there was a minimal risk of P losses via leaching in the medium term in the sandy forest soil because of the repeated biosolids application, particularly at the standard rate. Recommendations and Perspectives Application to low-fertility forest land can be used as an environmentally friendly option for biosolids management. When biosolids are applied at a rate to meet the N requirement of the tree crop, it can take a very long time before the forest soil is saturated with P. However, when a biosolids product contains high concentrations of P and is applied at a high rate, the forest ecosystem may not have the capacity to retain all P applied with biosolids in the long term. ESS-Submission Editor: Dr. Jean-Paul Schwitzguébel jean-paul.schwitzguebel@epfl.ch     

Comparison among model estimates of critical loads of acidic deposition using different sources and scales of input data

The critical load (CL) of acidic atmospheric deposition represents the load of acidity deposited from the atmosphere to the earth’s surface at which harmful acidification effects on sensitive biological receptors are thought to occur. In this study, the CL for forest soils was estimated for 27 watersheds throughout the United States using a steady-state mass balance approach based on both national and site-specific data and using different approaches for estimating base cation weathering. Results suggested that the scale and source of input data can have large effects on the calculated CL and that the most important parameter in the steady-state model used to estimate CL is base cation weathering. These results suggest that the data and approach used to estimate weathering must be robust if the calculated CL is to be useful for its intended purpose.     

Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Assessment of human health risks and pollution index for heavy metals in farmlands irrigated by effluents of stabilization ponds

Areas contaminated with heavy metals can pose major risks to human health and ecological environments. The aims of this study are to assess human health risk and pollution index for heavy metals in agricultural soils irrigated by effluents of stabilization ponds in Birjand, Iran. The results revealed that the levels of Cr, Mn, Zn, Fe, Cu, Cd, and Pb were in range of 70.3–149.65, 355–570, 31.15–98.45, 23,925–29,140, 22.75–25.95, 0.17–6.51, and 8.5–23.5 mg/kg in topsoils, respectively. Total hazard index values from heavy metals through three exposure routes for adults and children were 9.13E−01 and 1.10, respectively, indicating that there was non-carcinogenic risk for children. The total risk of carcinogenic metals (Cr, Cd, and Pb) through the three exposure routes for adults and children was 1.06E−04 and 9.76E−04, respectively, which indicates that the metals in the soil will not induce carcinogenic risks to these age groups. Pollution levels of heavy metals in soil samples including enrichment factor (EF), contamination factor (CF), pollution load index (PLI), and geo-accumulation index (Igeo) showed heavy metal contamination of agricultural soils. The results of the present study provide basic information about heavy metal contamination control and human health risk assessment management in the study area.