Using Cluster Analysis to Compartmentalize a Large Managed Wetland Based on Physical, Biological, and Climatic Geospatial Attributes.

Hierarchical and partitional cluster analyses were used to compartmentalize Water Conservation Area 1, a managed wetland within the Arthur R. Marshall Loxahatchee National Wildlife Refuge in southeast Florida, USA, based on physical, biological, and climatic geospatial attributes. Single, complete, average, and Ward's linkages were tested during the hierarchical cluster analyses, with average linkage providing the best results. In general, the partitional method, partitioning around medoids, found clusters that were more evenly sized and more spatially aggregated than those resulting from the hierarchical analyses. However, hierarchical analysis appeared to be better suited to identify outlier regions that were significantly different from other areas. The clusters identified by geospatial attributes were similar to clusters developed for the interior marsh in a separate study using water quality attributes, suggesting that similar factors have influenced variations in both the set of physical, biological, and climatic attributes selected in this study and water quality parameters. However, geospatial data allowed further subdivision of several interior marsh clusters identified from the water quality data, potentially indicating zones with important differences in function. Identification of these zones can be useful to managers and modelers by informing the distribution of monitoring equipment and personnel as well as delineating regions that may respond similarly to future changes in management or climate.

Physicochemical and sorptive properties of biochars derived from woody and herbaceous biomass.

It is unclear how the properties of biochar control its ability to sorb metals. In this work, physicochemical properties of a variety of biochars, made from four types of feedstock at three pyrolysis temperatures (300, 450 and 600°C) were compared to their ability to sorb arsenic (As) and lead (Pb) in aqueous solutions. Experimental results showed that both feedstock types and pyrolysis temperature affected biochar's production rate, i.e., ratio of mass of biochar and biomass, thermal stability, elemental composition, non-combustible component (NCC) content, pH values, surface areas and thus their sorption ability to the two metals in aqueous solution. In general, the high temperature biochars had low O/C and H/C ratios, were more carbonized with larger surface area, and were more concentrated with alkaline cations. In addition, biochars made from woody feedstocks had larger surface area, but lower NCC contents than that made from grasses under the same conditions. Although all the tested biochars removed both As and Pb from aqueous solutions, they showed different sorption abilities because of the variations in properties. Statistical analyses suggested that feedstock type affected the sorption ability of the biochars to both As and Pb significantly (p<0.001). Pyrolysis temperature, however, showed little influence on biochar sorption of Pb in aqueous solutions. Statistical analyses also showed that electrostatic interaction played an important role in controlling the sorption of both As(V) and Pb(II) onto the biochar. Other mechanisms, such as precipitation and surface complexation, could also control the sorption of Pb(II) onto the biochars.

Manganese oxide-modified biochars: preparation, characterization, and sorption of arsenate and lead.

This work explored two modification methods to improve biochar's ability to sorb arsenic (As) and lead (Pb). In one, pine wood feedstock was pyrolyzed in the presence of MnCl2·4H2O (MPB) and in the other it was impregnated with birnessite via precipitation following pyrolysis (BPB). The resulting biochars were characterized using thermogravimetry, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analyses. The dominant crystalline forms of Mn oxides in the MPB and BPB were manganosite and birnessite, respectively. Batch sorption studies were carried out to determine the kinetics and magnitude of As(V) and Pb(II) onto the biochars. As(V) and Pb(II) sorption capacities of MPB (0.59 and 4.91 g/kg) and BPB (0.91 and 47.05 g/kg) were significantly higher than that of the unmodified biochar (0.20 and 2.35 g/kg). BPB showed the highest sorption enhancement because of the strong As(V) and Pb(II) affinity of its birnessite particles.

Removal of arsenic by magnetic biochar prepared from pinewood and natural hematite.

There is a need for the development of low-cost adsorbents to removal arsenic (As) from aqueous solutions. In this work, a magnetic biochar was synthesized by pyrolyzing a mixture of naturally-occurring hematite mineral and pinewood biomass. The resulting biochar composite was characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). In comparison to the unmodified biochar, the hematite modified biochar not only had stronger magnetic property but also showed much greater ability to remove As from aqueous solution, likely because the γ-Fe2O3 particles on the carbon surface served as sorption sites through electrostatic interactions. Because the magnetized biochar can be easily isolated and removed with external magnets, it can be used in various As contaminant removal applications.

Linking Spatial Variations in Water Quality with Water and Land Management using Multivariate Techniques.

Most studies using multivariate techniques for pollution source evaluation are conducted in free-flowing rivers with distinct point and nonpoint sources. This study expanded on previous research to a managed "canal" system discharging into the Indian River Lagoon, Florida, where water and land management is the single most important anthropogenic factor influencing water quality. Hydrometric and land use data of four drainage basins were uniquely integrated into the analysis of 25 yr of monthly water quality data collected at seven stations to determine the impact of water and land management on the spatial variability of water quality. Cluster analysis (CA) classified seven monitoring stations into four groups (CA groups). All water quality parameters identified by discriminant analysis showed distinct spatial patterns among the four CA groups. Two-step principal component analysis/factor analysis (PCA/FA) was conducted with (i) water quality data alone and (ii) water quality data in conjunction with rainfall, flow, and land use data. The results indicated that PCA/FA of water quality data alone was unable to identify factors associated with management activities. The addition of hydrometric and land use data into PCA/FA revealed close associations of nutrients and color with land management and storm-water retention in pasture and citrus lands; total suspended solids, turbidity, and NO + NO with flow and Lake Okeechobee releases; specific conductivity with supplemental irrigation supply; and dissolved O with wetland preservation. The practical implication emphasizes the importance of basin-specific land and water management for ongoing pollutant loading reduction and ecosystem restoration programs.

Investigation of long-term trends in selected physical and chemical parameters of inflows to Everglades National Park, 1977-2005.

Data of seven water-quality parameters from inflows to the Everglades National Park were collected at three monitoring stations and analyzed for temporal trends. The best-fit models for the existence of trends were evaluated. The Kolmogorov-Smirnov test was used to select the theoretical distribution which best fit the data. Simple regression was used to examine the parameters for concentration-discharge relationships. The power and linear models were found to better describe the concentration-discharge relationships. Loess trend lines indicated a similar trend period of color value change during the selected period at three stations. The sharp decrease in color after 1990 at each station is consistent with the beneficial impacts of control measures, which include Best Management Practices implementation in the Everglades Agricultural Area, water management improvement, and the construction of additional stormwater treatment areas. The existence of trend analysis was performed by using the uncensored seasonal Kendall test. Conductivity and color decreased significantly at two (S12A and S333) of three stations. Alkalinity decreased significantly at S333. A "best-fit" model was selected to describe a trend change with statistical significance; the second-order equation provides a better description of the trend. This study also indicates that by using the routinely measured water-quality parameters, it may be easier to quantify the changes in water quality to aid in making water resources management decisions.

Nutrient discharges to Biscayne Bay, Florida: trends, loads, and a pollutant index.

Changes in land use, management practices, and environmental conditions may all lead to detectable differences in nutrients transported to aquatic systems. Biscayne Bay, an oligotrophic estuary in southeastern Florida, requires minimal phosphorus and nitrogen inputs and here we quantified the effects of continued watershed development. Nutrient (nitrate/nitrite-nitrogen [NO(X)-N], total ammonia nitrogen [NH(3)-N], and total phosphorus [TP]) water quality data (1992-2006) from six monitoring sites were evaluated using trend analysis, load estimation, and a new Pollutant Empower Density (PED) index. The PED index assesses the effect of discharged pollutants relative to the background productivity of aquatic environments. NO(X)-N, NH(3)-N, and TP concentrations declined or exhibited no change at most sites, with only six instances of significantly (p<0.1) increasing trends. Load estimates revealed higher NO(X)-N loads in the southern, agricultural section of the watershed and higher NH(3)-N and TP loads in the urbanized northern and central areas. NO(X)-N loads from site MW04 (south) were the highest for all sites while site LR06 (north) had the highest NH(3)-N and TP loads. Of the evaluated canal discharges, PED index values also suggested that canal discharges from these two sites (MW04 and LR06) had the greatest potential for impact in the bay. Overall, water quality is generally improving but canal discharges are coupled with land use activities in adjacent drainage areas. Trend analysis, load estimation, and the PED index can be used together to provide a more holistic interpretation of water quality, which is necessary for optimizing resources to meet watershed management goals.

Contribution of wastewater treatment plant effluents to nutrient dynamics in aquatic systems: a review.

Excessive nutrient loading (considering nitrogen and phosphorus) is a major ongoing threat to water quality and here we review the impact of nutrient discharges from wastewater treatment plants (WWTPs) to United States (U.S.) freshwater systems. While urban and agricultural land uses are significant nonpoint nutrient contributors, effluent from point sources such as WWTPs can overwhelm receiving waters, effectively dominating hydrological characteristics and regulating instream nutrient processes. Population growth, increased wastewater volumes, and sustainability of critical water resources have all been key factors influencing the extent of wastewater treatment. Reducing nutrient concentrations in wastewater is an important aspect of water quality management because excessive nutrient concentrations often prevent water bodies from meeting designated uses. WWTPs employ numerous physical, chemical, and biological methods to improve effluent water quality but nutrient removal requires advanced treatment and infrastructure that may be economically prohibitive. Therefore, effluent nutrient concentrations vary depending on the particular processes used to treat influent wastewater. Increasingly stringent regulations regarding nutrient concentrations in discharged effluent, along with greater freshwater demand in populous areas, have led to the development of extensive water recycling programs within many U.S. regions. Reuse programs provide an opportunity to reduce or eliminate direct nutrient discharges to receiving waters while allowing for the beneficial use of reclaimed water. However, nutrients in reclaimed water can still be a concern for reuse applications, such as agricultural and landscape irrigation.