Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review

NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250m, but less than 1000m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.     

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier.     

Physicochemical controls on initiation and evolution of desiccation cracks in sand-bentonite mixtures: X-ray CT imaging and stochastic modeling

The shrink-swell behavior of active clays in response to changes in physicochemical conditions creates great challenges for construction of geotechnical barriers for hazardous waste isolation, and is of significant importance for management of agricultural and natural resources. Initiation and evolution of desiccation cracks in active clays are strongly dependent on physicochemical initial and boundary conditions. To investigate effects of bentonite content (20, 40, 60%), pore fluid chemistry (0.05 and 0.5M NaCl) and drying rates (40 and 60°C) on cracking behavior, well-controlled dehydration experiments were conducted and X-ray Computed Tomography (CT) was applied to visualize and quantify geometrical features of evolving crack networks. A stochastic model based on the Fokker-Plank equation was adopted to describe the evolution of crack aperture distributions (CAD) and to assess the impact of physicochemical factors on cracking behavior. Analyses of crack porosity and crack specific surface area showed that both clay content and temperature had larger impact on cracking than pore fluid concentration. More cracks formed at high bentonite contents (40 and 60%) and at high drying rate (60°C). The drift, diffusion and source terms derived from stochastic analysis indicated that evaporative demand had greater influence on the dynamics of the CAD than solution chemistry.     

Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.     

Sociodemographic, reproductive and dietary predictors of organochlorine compounds levels in pregnant women in Spain

Organochlorine pesticides and polychlorinated biphenyls (PCBs) are consistently found in human tissues. Serum levels of organochlorine compounds (OC) in pregnant women in particular have raised concern about possible harm to humans in the early phases of physical and behavioural development. The objective of the present study was to evaluate the association between concentration of OCs in serum of two cohorts of pregnant women from Gipuzkoa and Sabadell in Spain and socioeconomic, reproductive and dietary variables. Concentration of polychlorinated biphenyls (PCBs: 28, 52, 101, 118, 138, 153 and 180), hexachlorobenzene (HCB), beta and gamma-hexachlorocyclohexane (β-HCH and γ-HCH), heptachlor epoxide, dichlorodiphenyl dichloroethylene (p,p'-DDE) and dichlorodiphenyl trichloroethane (p,p'-DDT) were measured in the serum of 1259 pregnant women. Associations between OCs and potential predictor variables were assessed using linear regression models adjusted for potential confounders. The compounds most commonly found in the serum were p,p'-DDE (99% of the samples) and PCB-153 (95% of the samples). Geometric means of serum concentrations (ng g?1 lipid) of organochlorine pesticides were 110.0, 19.1, and 33.5 for p,p'-DDE, β-HCH, and HCB respectively, while the geometric means of PCBs were 21.8, 38.9 and 26.9 for PCB 138, 153, and 180 respectively. The levels of all OCs increased with age. BMI was positively associated with the concentration of organochlorine pesticides but inversely related to PCB concentrations. The serum levels of OCs fell only after a cumulative period of breastfeeding of over a year. Levels of PCBs were related to fish intake, but in general dietary factors did not improve the explained variability of the concentrations of OCs. Overall, the levels of OCs found in the study are at the lower end of the range reported in Spain and other countries.     

Integrated biological responses of zebrafish (Danio rerio) to analyze water quality in regions under anthropogenic influence

This study analyzed water quality in regions around Patos lagoon (Southern Brazil) that are under anthropogenic pressure. Water samples were collected from five different sites, including one used as a source for human consumption (COR) and others known to be influenced by human activities (IP). Danio rerio (Teleostei, Cyprinidae) organisms were exposed for 24 h to these water samples, plus a control group. It was observed that: (1) reactive oxygen species levels were lower in COR and IP than in the control group; (2) glutamate-cysteine ligase (catalytic subunit) expression was higher in COR than in other sites; (3) exposure to all water samples affected long-term memory (LTM) when compared to control group. Thus, some water samples possess the ability to modulate the antioxidant system and to induce a decline in cognitive functions, as measured by LTM. The obtained results indicate that a combination of variables of different organization level (molecular, biochemical and behavioral) can be employed to analyze water quality in impacted regions.     

Is black carbon a better predictor of polycyclic aromatic hydrocarbon distribution in soils than total organic carbon?

Black carbon (BC) and total organic carbon (TOC) were quantified in the surface soils of Switzerland (N = 105) and Delhi (N = 36), India, to examine their relationships with contents of polycyclic aromatic hydrocarbons (PAH). BC content in Swiss (background) soils (N = 104) varied from 0.41 to 4.75 mg/g (median: 1.13 mg/g) and constituted 1-9% (median: 3%) of TOC. Indian (urban) soils had similar BC concentrations (0.37-2.05 mg/g, median: 1.19 mg/g), with relatively higher BC/TOC (6-23%, median: 13%). Similar to TOC, BC showed significant positive correlation with lighter PAH, but no correlation with heavier PAH in Swiss soils. In contrast, heavier PAH were significantly correlated only with BC in Delhi soils. It seems that TOC governs the distribution of PAH in organic matter rich background soils, while the proximity to emission sources is reflected by BC-PAH association in urban soils.     

Integrated analysis of the effects of agricultural management on nitrogen fluxes at landscape scale

The integrated modelling system INITIATOR was applied to a landscape in the northern part of the Netherlands to assess current nitrogen fluxes to air and water and the impact of various agricultural measures on these fluxes, using spatially explicit input data on animal numbers, land use, agricultural management, meteorology and soil. Average model results on NH₃ deposition and N concentrations in surface water appear to be comparable to observations, but the deviation can be large at local scale, despite the use of high resolution data. Evaluated measures include: air scrubbers reducing NH₃ emissions from poultry and pig housing systems, low protein feeding, reduced fertilizer amounts and low-emission stables for cattle. Low protein feeding and restrictive fertilizer application had the largest effect on both N inputs and N losses, resulting in N deposition reductions on Natura 2000 sites of 10% and 12%, respectively.     

Assessing the recovery potential of alpine moss-sedge heath: reciprocal transplants along a nitrogen deposition gradient

The potential of alpine moss-sedge heath to recover from elevated nitrogen (N) deposition was assessed by transplanting Racomitrium lanuginosum shoots and vegetation turfs between 10 elevated N deposition sites (8.2-32.9 kg ha⁻¹ yr⁻¹) and a low N deposition site, Ben Wyvis (7.2 kg ha⁻¹ yr⁻¹). After two years, tissue N of Racomitrium shoots transplanted from higher N sites to Ben Wyvis only partially equilibrated to reduced N deposition whereas reciprocal transplants almost matched the tissue N of indigenous moss. Unexpectedly, moss shoot growth was stimulated at higher N deposition sites. However, moss depth and biomass increased in turfs transplanted to Ben Wyvis, apparently due to slower shoot turnover (suggested to result partly from decreased tissue C:N slowing decomposition), whilst abundance of vascular species declined. Racomitrium heath has the potential to recover from the impacts of N deposition; however, this is constrained by the persistence of enhanced moss tissue N contents.