Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Park isolation in anthropogenic landscapes: land change and livelihoods at park boundaries in the African Albertine Rift

Regional Environmental Change - Landscapes are changing rapidly in regions where rural people live adjacent to protected parks and reserves. This is the case in highland East Africa, where many...     

Release of nitrogen and trace metal species from field stacked biosolids

Concerns over elevated nitrate (NO3-) levels found in groundwater near former biosolid stockpiling locations resulted in the Maine Department of Environmental Protection (MDEP) imposing stricter regulations governing the stockpiling of biosolids in October 2002. The goals of this study were to measure the amount and speciation of nitrogen (N) and trace metals leaving stockpiled biosolids and travelling through the soil column. The biosolids were placed on plastic-lined cells to collect all leachate. Ammonium (NH4+), ranging from 2000 to 4900 mg L(-1), was the dominant N species (90% of total N) in the leachate from the Class B lime-stabilized biosolids in the lined cell experiment. Nitrate (NO3-) and nitrite (NO2-) concentrations were negligible, remaining below 0.25 and 0.1 mg L(-1), respectively. Dissolved organic carbon (DOC) concentrations as high as 8900 mg L(-1) and chemical oxygen demand (COD) as high as 37 000 mg L(-1) were measured in the leachate leaving the lined cell. Fifteen zero-tension pan lysimeters (ZTP-lysimeter) were installed in a 90 m2 plot at depth intervals of 30, 60, and 100 cm. Leachate passing through the soil column underlying the biosolids stockpile was collected in the ZTP-lysimeters. The average ZTP-lysimeter NH4+ concentrations ranged from 1400 mg L(-1) at 60 cm depth to 145 mg L(-1) at 90 cm depth. The average ZTP-lysimeter DOC concentrations ranged from 2000 mg L(-1) at 60 cm to 525 mg L(-1) at 90 cm. Trace metal determinations of the leachate collected from the lined cell and ZTP-lysimeters showed arsenic loading rates exceeded the state limits of 0.5 kg ha(-1) year(-1) by an order of magnitude. Arsenic concentrations were in excess of several thousand milligrams per litre in the lined-cell leachate and several hundred milligrams per litre in the ZTP-lysimeters as deep as 90 cm under the biosolid stockpile. Phosphorus, iron and manganese in excess of several thousand milligrams per litre were observed in both the lined-cell leachate and ZTP-lysimeters. Significant concentrations of other trace metals were found at depth in the zero-tension ZTP-lysimeter plot. Trace metals were largely mobilized by the DOC from the biosolids and due to the presence of anaerobic environment, especially in the underlying soil.     

Application of Artificial Neural Networks to Predict Total Dissolved Solids at the Karaj Dam

We applied multilayer perceptron (MLP) and radial basis function (RBF) neural networks using data from two water quality monitoring stations at the Karaj Dam in Iran. Input data were calcium ions (Ca²⁺), magnesium ions (Mg²⁺), sodium ions (Na⁺), chloride ions (Cl^?), sulfate (), and pH, and the output data were total dissolved solids (TDS). An MLP with one hidden layer containing eight neurons was selected for the upstream water quality station using normalized input data. We developed a second MLP neural network for the downstream station with one hidden layer containing 10 neurons in the hidden layer using normalized input data. Considering applying normalized input data and one hidden layer, the coefficient of determination (R ²) and index of agreement (IA) between the observed and the predicted data for the upstream and downstream monitoring stations using the MLP neural networks were 0.985, 0.84, 0.99, and 0.92, respectively. The RBF neural network with 100 neurons in its hidden layer reached the minimum errors between the observed and the predicted results in upstream and downstream stations. The R ² between observed and predicted data for upstream and downstream monitoring stations for the RBF was 0.999 and 0.998, respectively. Data normalization improved the performance of the MLP neural networks. Sensitivity analysis indicated that magnesium is the most effective water quality parameter for predicting TDS, and sulfate is the second most effective water quality parameter affecting TDS prediction at the Karaj Dam.     

Predicting Particulate Matter (PM2.5) Concentrations in the Air of Shahr‐e Ray City,Iran, by Using an Artificial Neural Network

Particulate matter (PM), along with other air pollutants, pose serious hazards to human health. The Artificial Neural Network (ANN) is a branch of artificial intelligence that has an ability to make accurate predictions. In this article, the authors describe such methods and how historical data on air quality, moisture, wind velocity, and temperature in Shahr‐e Ray City, located at the southern tip of Tehran, was used to train an ANN to provide accurate predictions of PM concentrations. The availability of such predictions can offer significant assistance to those who are working to reduce air pollution.     

Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA

In the present study, the BCR (Community Bureau of Reference) sequential procedure has been applied to determine the zinc partition in sediments taken from a river situated in the Southwest of Romania, in a region subject of intense mining activities. The sampling was performed during three sampling expeditions, organized in the spring, summer, and autumn, 2007. The zinc concentration in different fractions was normalized, its concentration being related to the concentrations of some metals (such as Al or Fe) that are naturally present in sediments. The zinc-contaminated sediments from the investigated area have been evaluated by means of combining the analysis data from the BCR sequential extraction with the normalization to the Al content. The most important zinc collector in the samples taken during the three sampling expeditions is the easily soluble fraction, next being amorphous iron and manganese hydrated oxides fraction, followed by organic matter fraction.     

Mobilization of metals and phosphorus from intact forest soil cores by dissolved inorganic carbon

Increased dissolved inorganic carbon (DIC) enhances the mobilization of metals and nutrients in soil solutions. Our objective was to investigate the mobilization of Al, Ca, Fe, and P in forest soils due to fluctuating DIC concentrations. Intact soil cores were taken from the O and B horizons at the Bear Brook Watershed in Maine (BBWM) to conduct soil column transport experiments. Solutions with DIC concentrations (～20–600 ppm) were introduced into the columns. DIC was reversibly sorbed and its migration was retarded by a factor of 1.2 to 2.1 compared to the conservative sodium bromide tracer, corresponding to a log K _D?=???0.82 to ?0.07. Elevated DIC significantly enhanced the mobilization of all Al, Fe, Ca, and P. Particulate (>0.4 μm) Al and Fe were mobilized during chemical and flow transitions, such as increasing DIC and dissolved organic carbon (DOC), and resumption of flow after draining the columns. Calcium and P were primarily in dissolved forms. Mechanisms such as ion exchange (Al, Fe, Ca), ligand- and proton-promoted dissolution (Al and Fe), and ligand exchange (P) were the likely chemical mechanisms for the mobilization of these species. One column was packed with dried and sieved B-horizon soil. The effluent from this column had DOC, Al, and Fe concentrations considerably higher than those in the intact columns, suggesting that these species were mobilized from soil’s microporous structure that was otherwise not exposed to the advective flow. Calcium and P concentrations, however, were similar to those in the intact columns, suggesting that these elements were less occluded in soil particles.     

Watershed Nitrogen and Mercury Geochemical Fluxes Integrate Landscape Factors in Long-term Research Watersheds at Acadia National Park, Maine, USA

This paper is an overview of this special issue devoted to watershed research in Acadia National Park (Acadia NP). The papers address components of an integrated research program on two upland watersheds at Acadia NP, USA (44° 20′ N latitude; 68° 15′ E longitude). These watersheds were instrumented in 1998 to provide a long-term foundation for regional ecological and watershed research. The research was initiated as part of EPA/NPS PRIMENet (Park Research and Intensive Monitoring of Ecosystems Network), a system of UV-monitoring stations and long-term watershed research sites located in US national parks. The initial goals at Acadia NP were to address research questions about mercury, acid rain, and nitrogen saturation developed from prior research. The project design was based on natural differences in forests and soils induced by an intense wildfire in one watershed in 1947. There is no evidence of fire in the reference watershed for several hundred years. We are testing hypotheses about controls on surface water chemistry, and bioavailability of contaminants in the contrasting watersheds. The unburned 47-ha Hadlock Brook watershed is 70% spruce-fir mature conifer forest. In contrast, burned 32-ha Cadillac Brook watershed, 4 km northeast of the Hadlock watershed, is 20% regenerating mixed northern hardwoods and 60% shrub/rocky balds. Differences in atmospheric deposition are controlled primarily by forest stand composition and age. The watersheds are gauged and have water chemistry stations at 122 m (Cadillac) and 137 m (Hadlock); watershed maximum elevations are 468 and 380 m, respectively. The stream water chemistry patterns reflect, in part, the legacy of the intense fire, which, in turn, controls differences in forest vegetation and soil characteristics. These factors result in higher nitrogen and mercury flux from the unburned watershed, reflecting differences in atmospheric deposition, contrasting ecosystem pools of nitrogen and mercury, and inferred differences in internal cycling and bioavailabilty.     

Dynamics of P, Al, and Fe during High Discharge Episodic Acidification at the Bear Brook Watershed in Maine, U.S.A.

Phosphorus (P), aluminum (Al), and iron (Fe) stream chemistry were assessed for high discharge snowmelt events at the Bear Brook Watershed, Maine (BBWM) during December 2001 and February 2002 and compared with results from a January 1995 study of the same streams. The West Bear catchment has been subjected to artificial acidification since 1989. The East Bear catchment is the untreated reference. Total (acid soluble) Al, Fe, and P were positively correlated with discharge during the 2001–2002 events. However, dissolved P concentrations remained low (≤0.1 μmol L^-1) during high discharge events as pH decreased in both streams.For example, in 2001, total P concentration increased to 1.7 μmol L^-1 during the rising limb of the hydrograph in West Bear, approximately five times the value in East Bear. During the same event, in West Bear and East Bear dissolved Al concentrations increased to 21 and 6.3 μmol L^-1, respectively, while total Al concentrations increased to 166 and 30 μmol L^-1, respectively. Dissolved Fe concentrations remained ≤0.9 μmol L^-1 in both streams during all study events. However, total Fe concentrations in 2001 increased to 239 and 4.1 μmol L^-1 for West Bear and East Bear, respectively. Total Al and Fe declined parallel to total P after peaking during all study periods. Nearly all of the base cations were in dissolved form during the three events, indicating that total Al in West and East Bear Brooks is not associated with primary minerals such as feldspars. We conclude that particulate Al, Fe, and P are chemically linked during transport at high discharge in these episodically and chronically acidified streams.     

Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column.The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))).In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction.The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).