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Partition coefficients of organic contaminants with carbohydrates

In view of the current lack of reliable partition coefficients for organic compounds with carbohydrates ( K ch ), carefully measured values with cellulose and starch, the two major forms of carbohydrates, are provided for a wide range of compounds: short-chain chlorinated hydrocarbons, halogenated benzenes, alkyl benzenes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and organochlorine pesticides. To ensure the accuracy of the K ch data, solute concentrations in both water and carbohydrate phases are measured by direct solvent extraction of the samples. For a given compound, the observed partition coefficient with cellulose ( K cl ) is virtually the same as that with starch ( K st ). This finding expedites the evaluation of organic contamination with different forms of carbohydrates. The presently determined K ch values of 13 PAHs are substantially lower (by 3−66 times) than the literature data; the latter are suspect as they were obtained with (i) presumably impure carbohydrate samples or (ii) indirectly measured equilibrium solute concentrations in carbohydrate and water phases. Although the K ch values are generally considerably lower than the respective K ow (octanol−water) or K lipid (lipid−water), accurate K ch data are duly required to accurately estimate the contamination of carbohydrates by organic compounds because of the abundance of carbohydrates over lipids in crops and plants. To overcome the current lack of reliable K ch data for organic compounds, a close correlation of log K ch with log K ow has been established for predicting the unavailable K ch data for low-polarity compounds.

Environmental Science and Technology↗

Immediate and long-term fire effects on total mercury in forests soils of northeastern Minnesota

Within the Boundary Waters Canoe Area Wilderness in northeastern Minnesota, soils were collected from 116 sites in areas of primarily virgin forest with fire-origin stand years (year of last recognizable stand-killing wildfire) that range from the 1759 to 1976. Median concentrations for total mercury in soils for this span of 217 years range from 0.28 ± 0.088 ppm (1759) to 0.09 ± 0.047 ppm (1976) for A-horizon soils and from 0.23 ± 0.062 ppm (1759) to 0.09 ± 0.018 ppm (1976) for O-horizon soils. A separate study of soils collected from 30 sites within an area that burned in a 2004 wildfire at Voyageurs National Park, northern Minnesota, suggested that high soil burn severity resulted in significant mercury loss from both organic and mineral soils. Integrated data from these two studies and additional regional soil data demonstrate that older forests have progressively higher mercury concentrations in O-horizon soils (r 2 = 0.423) and A-horizon soils (r 2 = 0.456). These results support the hypotheses that an important factor for mercury concentrations in forest soils is time since stand-replacing fire and that high soil burn severity has the potential to reduce the concentration of mercury in burned soils for tens to hundreds of years.

Minnesota↗

Zinc isotopic signatures in eight lake sediment cores from across the United States

Zinc is an important trace element pollutant in urban environments; however, the extent of Zn contamination and the sources of urban Zn pollution are often unclear. We measured Zn concentrations and isotopes in sediment cores collected from eight lakes or reservoirs across the United States. We paired these data with historical records of land use within each watershed to calculate a mean Zn concentration and δ 66 Zn for natural (less than 5% urban land use; 123 ± 21.7 mg/kg; +0.33 ± 0.08‰, n = 6 lakes) and urban (greater than 70% urban land use; 389 ± 200 mg/kg; +0.14 ± 0.07‰, n = 3 lakes) lake sediments. The relation between Zn concentration data and Zn isotope data allows us to create a mixing model between two end members: natural and urban. The δ 66 Zn of the urban end-member is consistent with Zn pollution from vehicle-related sources (tire wear and emissions). Application of this model to samples collected from lakes recording periods ranging from 5 to 70% urban land use in their surrounding watersheds indicates that the lakes and reservoirs were affected by large amounts of Zn from urban sources.

conterminous United States↗

Relating carbon monoxide photoproduction to dissolved organic matter functionality

Aqueous solutions of humic substances (HSs) and pure monomeric aromatics were irradiated to investigate the chemical controls upon carbon monoxide (CO) photoproduction from dissolved organic matter (DOM). HSs were isolated from lakes, rivers, marsh, and ocean. Inclusion of humic, fulvic, hydrophobic organic, and hydrophilic organic acid fractions from these environments provided samples diverse in source and isolation protocol. In spite of these major differences, HS absorption coefficients (a) and photoreactivities (a bleaching and CO production) were strongly dependent upon HS aromaticity ( r 2 >0.90; n = 11), implying aromatic moieties are the principal chromophores and photoreactants within HSs, and by extension, DOM. Carbonyl carbon and CO photoproduction were not correlated, implying that carbonyl moieties are not quantitatively important in CO photoproduction. CO photoproduction efficiency of aqueous solutions of monomeric aromatic compounds that are common constituents of organic matter varied with the nature of ring substituents. Specifically, electron donating groups increased, while electron withdrawing groups decreased CO photoproductivity, supporting our conclusion that carbonyl substituents are not quantitatively important in CO photoproduction. Significantly, aromatic CO photoproduction efficiency spanned 3 orders of magnitude, indicating that variations in the CO apparent quantum yields of natural DOM may be related to variations in aromatic DOM substituent group chemistry.

Environmental Science and Technology↗

The Western Airborne Contaminant Assessment Project (WACAP): An interdisciplinary evaluation of the impacts of airborne contaminants in Western U.S. National Parks

The concept of a nature reserve such as a National Park is to maintain a location for the enjoyment and study of a pristine environment. However, many pollutants are now known to spread far and wide from their (point[s] of) origin. To grasp the extent of pervasive and boundary-less pollution, the ambitious WACAP study evaluated contaminant data collected from Western U.S. National Parks in various media. In this Feature, Landers et al. summarize the report and speak to its utility moving forward.

Environmental Science and Technology↗

Transport, behavior, and fate of volatile organic compounds in streams

Volatile organic compounds (VOCs) are compounds with chemical and physical properties that allow the compounds to move freely between the water and air phases of the environment. VOCs are widespread in the environment because of this mobility. Many VOCs have properties that make them suspected or known hazards to the health of humans and aquatic organisms. Consequently, understanding the processes affecting the concentration and distribution of VOCs in the environment is necessary. The transport, behavior, and fate of VOCs in streams are determined by combinations of chemical, physical, and biological processes. These processes are volatilization, absorption, wet and dry deposition, microbial degradation, sorption, hydrolysis, aquatic photolysis, oxidation, chemical reaction, biocon-centration, advection, and dispersion. The relative importance of each of these processes depends on the characteristics of the VOC and the stream. The U.S. Geological Survey National Water-Quality Assessment Program selected 55 VOCs for study. This article reviews the characteristics of the various processes that could affect the transport, behavior, and fate of these VOCs in streams.

Critical Reviews in Environmental Science and Tech↗

The role of the Everglades Mangrove Ecotone Region (EMER) in regulating nutrient cycling and wetland productivity in South Florida

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw −1 ) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (∼1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.

Florida↗

Biogeochemical processes on tree islands in the greater everglades: Initiating a new paradigm

Scientists’ understanding of the role of tree islands in the Everglades has evolved from a plant community of minor biogeochemical importance to a plant community recognized as the driving force for localized phosphorus accumulation within the landscape. Results from this review suggest that tree transpiration, nutrient infiltration from the soil surface, and groundwater flow create a soil zone of confluence where nutrients and salts accumulate under the head of a tree island during dry periods. Results also suggest accumulated salts and nutrients are flushed downstream by regional water flows during wet periods. That trees modulate their environment to create biogeochemical hot spots and strong nutrient gradients is a significant ecological paradigm shift in the understanding of the biogeochemical processes in the Everglades. In terms of island sustainability, this new paradigm suggests the need for distinct dry-wet cycles as well as a hydrologic regime that supports tree survival. Restoration of historic tree islands needs further investigation but the creation of functional tree islands is promising.

Florida↗

Influence of changing water sources and mineral chemistry on the everglades ecosystem

Human influences during the previous century increased mineral inputs to the Florida Everglades by changing the sources and chemistry of surface inflows. Biogeochemical responses to this enrichment include changes in the availability of key limiting nutrients such as P, the potential for increased turnover of nutrient pools due to accelerated plant decomposition, and increased rates of mercury methylation associated with sulfate enrichment. Mineral enrichment has also been linked to the loss of sensitive macrophyte species, although dominant Everglades species appear tolerant of a broad range of mineral chemistry. Shifts in periphyton community composition and function provide an especially sensitive indicator of mineral enrichment. Understanding the influence of mineral chemistry on Everglades processes and biota may improve predictions of ecosystem responses to ongoing hydrologic restoration efforts and provide guidelines for protecting remaining mineral-poor areas of this peatland.

Florida↗

Dissolved organic matter in the Florida everglades: Implications for ecosystem restoration

Dissolved organic matter (DOM) in the Florida Everglades controls a number of environmental processes important for ecosystem function including the absorption of light, mineral dissolution/precipitation, transport of hydrophobic compounds (e.g., pesticides), and the transport and reactivity of metals, such as mercury. Proposed attempts to return the Everglades to more natural flow conditions will result in changes to the present transport of DOM from the Everglades Agricultural Area and the northern conservation areas to Florida Bay. In part, the restoration plan calls for increasing water flow throughout the Everglades by removing some of the manmade barriers to flow in place today. The land- and water-use practices associated with the plan will likely result in changes in the quality, quantity, and reactivity of DOM throughout the greater Everglades ecosystem. The authors discuss the factors controlling DOM concentrations and chemistry, present distribution of DOM throughout the Everglades, the potential effects of DOM on key water-quality issues, and the potential utility of dissolved organic matter as an indicator of success of restoration efforts.

Florida↗

Sulfur in the South Florida ecosystem: Distribution, sources, biogeochemistry, impacts, and management for restoration

Sulfur is broadly recognized as a water quality issue of significance for the freshwater Florida Everglades. Roughly 60% of the remnant Everglades has surface water sulfate concentrations above 1 mg l-1, a restoration performance measure based on present sulfate levels in unenriched areas. Highly enriched marshes in the northern Everglades have average sulfate levels of 60 mg l-1. Sulfate loading to the Everglades is principally a result of land and water management in South Florida. The highest concentrations of sulfate (average 60-70 mg l-1) in the ecosystem are in canal water in the Everglades Agricultural Area (EAA). Potential sulfur sourcesin the watershed are many, but geochemical data and a preliminary sulfur mass balance for the EAA are consistent with sulfur presently used in agricultural, and sulfur released by oxidation of organic EAA soils (including legacy agricultural applications and natural sulfur) as the primary sources of sulfate enrichment in the EAA canals. Sulfate loading to the Everglades increases microbial sulfate reduction in soils, leading to more reducing conditions, greater cycling of nutrients in soils, production of toxic sulfide, and enhanced methylmercury (MeHg) production and bioaccumulation. Wetlands are zones of naturally high MeHg production, but the combination of high atmospheric mercury deposition rates in South Florida and elevated sulfate loading leads to increased MeHg production and MeHg risk to Everglades wildlife and human consumers. Sulfate from the EAA drainage canals penetrates deep into the Everglades Water Conservation Areas, and may extend into Everglades National Park. Present plans to restore sheet flow and to deliver more water to the Everglades may increase overall sulfur loads to the ecosystem, and move sulfate-enriched water further south. However, water management practices that minimize soil drying and rewetting cycles can mitigate sulfate release during soil oxidation. A comprehensive Everglades restoration strategy should include reduction of sulfur loads as a goal because of the many detrimental impacts of sulfate on the ecosystem. Monitoring data show that the ecosystem response to changes in sulfate levels is rapid, and strategies for reducing sulfate loading may be effective in the near term. A multifaceted approach employing best management practices for sulfur in agriculture, agricultural practices that minimize soil oxidation, and changes to stormwater treatment areas that increase sulfate retention could help achieve reduced sulfate loads to the Everglades, with resulting benefits.

Florida↗

Recent and historic drivers of landscape change in the Everglades ridge, slough, and Tree Island mosaic

More than half of the original Everglades extent formed a patterned peat mosaic of elevated ridges, lower and more open sloughs, and tree islands aligned parallel to the dominant flow direction. This ecologically important landscape structure remained in a dynamic equilibrium for millennia prior to rapid degradation over the past century in response to human manipulation of the hydrologic system. Restoration of the patterned landscape structure is one of the primary objectives of the Everglades restoration effort. Recent research has revealed that three main drivers regulated feedbacks that initiated and maintained landscape structure: the spatial and temporal distribution of surface water depths, surface and subsurface flow, and phosphorus supply. Causes of recent degradation include but are not limited to perturbations to these historically important controls; shifts in mineral and sulfate supply may have also contributed to degradation. Restoring predrainage hydrologic conditions will likely preserve remaining landscape pattern structure, provided a sufficient supply of surface water with low nutrient and low total dissolved solids content exists to maintain a rainfall-driven water chemistry. However, because of hysteresis in landscape evolution trajectories, restoration of areas with a fully degraded landscape could require additional human intervention.

Critical Reviews in Environmental Science and Tech↗

Transport and fate of microbial pathogens in agricultural settings

An understanding of the transport and survival of microbial pathogens (pathogens hereafter) in agricultural settings is needed to assess the risk of pathogen contamination to water and food resources, and to develop control strategies and treatment options. However, many knowledge gaps still remain in predicting the fate and transport of pathogens in runoff water, and then through the shallow vadose zone and groundwater. A number of transport pathways, processes, factors, and mathematical models often are needed to describe pathogen fate in agricultural settings. The level of complexity is dramatically enhanced by soil heterogeneity, as well as by temporal variability in temperature, water inputs, and pathogen sources. There is substantial variability in pathogen migration pathways, leading to changes in the dominant processes that control pathogen transport over different spatial and temporal scales. For example, intense rainfall events can generate runoff and preferential flow that can rapidly transport pathogens. Pathogens that survive for extended periods of time have a greatly enhanced probability of remaining viable when subjected to such rapid-transport events. Conversely, in dry seasons, pathogen transport depends more strongly on retention at diverse environmental surfaces controlled by a multitude of coupled physical, chemical, and microbiological factors. These interactions are incompletely characterized, leading to a lack of consensus on the proper mathematical framework to model pathogen transport even at the column scale. In addition, little is known about how to quantify transport and survival parameters at the scale of agricultural fields or watersheds. This review summarizes current conceptual and quantitative models for pathogen transport and fate in agricultural settings over a wide range of spatial and temporal scales. The authors also discuss the benefits that can be realized by improved modeling, and potential treatments to mitigate the risk of waterborne disease transmission.

Critical Reviews in Environmental Science and Tech↗

A review of algal toxin exposures on reserved federal lands and among trust species in the United States

Associated health effects from algal toxin exposure are a growing concern for human and animal health. Algal toxin poisonings may occur from contact with or consumption of water supplies or from ingestion of contaminated animals. The U.S. Federal Government owns or holds in trust about 259 million hectares of land, in addition to the Trust species obligations. We completed the first comprehensive review of potential toxin-producing algal blooms in surface waters on Federal lands and Trust species exposed to algal toxins. Events were sorted into three tiers based on potentially toxic algae abundance or toxin concentration and related effects on animal morbidity and mortality. At least 11.1% of Federal lands are known to have been affected by algal events, but exposure is likely underreported. The occurrence of potential toxin producers and their toxins (Tier 1) have been documented 337 times, health advisory threshold exceedances (Tier 2) were reported 943 times, and 86 events involved animal sickness or death linked to cyanobacteria or marine toxins (Tier 3). Trust species exposed to cyano- or algal toxins included marine mammals, migratory birds, threatened and endangered species, and species of concern. We report numerous data gaps ranging from potential effects on human health from consuming intoxicated animals to the infrequency of measuring and reporting certain toxins. Improvements to field and laboratory methods, more consistent evaluation of toxin exposure, decreased latency on data analysis, delivery and interpretation will be necessary to improve response and management strategies for protecting human and animal health where issues persist.

Critical Reviews in Environmental Science and Tech↗

Critical review of mercury methylation and methylmercury demethylation rate constants in aquatic sediments for biogeochemical modeling

Mercury is a toxin that causes neurological impairments in adults, is particularly harmful for fetuses and children, and is deadly in severe cases, making it a worldwide health concern. Methylmercury (MeHg) is the environmentally relevant form of mercury (Hg) because it biomagnifies along the food chain. Methylmercury is mainly produced in aquatic sediments via methylation of inorganic Hg (Hg(II)) and transformed back via demethylation. Because transformation rates determine MeHg concentrations, quantification of methylation and demethylation rates is needed to inform management of MeHg. Published rate constants for Hg(II) methylation ( 𝑘 𝑚 ) and MeHg demethylation ( 𝑘 𝑑 ) vary greatly, stemming partly from differences in experimental methods. We conducted a comprehensive review of rate laws, evaluated published rate constants, and performed biogeochemical simulations to assess variability in reported 𝑘 𝑚 and 𝑘 𝑑 . Based on selected studies employing the same pseudo-first-order rate law and similar experimental methods, we found that 𝑘 𝑚 = 0.04 ± 0.03 d −1 is a reasonable range for wetland sediments. Over a number of environments, maximum 𝑘 𝑑 was smaller at sites without Hg source ( 𝑘 𝑑 = 0.5 d −1 ) than at sites with identified Hg source ( 𝑘 𝑑 = 1.8 d −1 ). Larger variability and higher uncertainty in 𝑘 𝑑 compared to 𝑘 𝑚 highlight the need for more research on MeHg demethylation rates. This critical review: (a) aids the design of future experimental studies of 𝑘 𝑚 and 𝑘 𝑑 ; (b) provides guidance for comparing rate constants from different studies; (c) presents a biogeochemical reaction model to assess rate constants; and (d) informs selection of 𝑘 𝑚 and 𝑘 𝑑 values from the literature for use in model simulations.

Critical Reviews in Environmental Science and Tech↗

Selected applications of hydrologic science and research in Maryland, Delaware, and Washington, D.C., 2001-2003

One of the roles of the U.S. Geological Survey (USGS) is to provide reliable water data and unbiased water science needed to describe and understand the Nation?s water resources. This fact sheet describes selected techniques that were used by the USGS to collect, transmit, evaluate, or interpret data, in support of investigations that describe the quantity and quality of water resources in Maryland (MD), Delaware (DE), and the District of Columbia (D.C.). These hydrologic investigations generally were performed in cooperation with universities, research centers, and other Federal, State, and local Government agencies. The applications of hydrologic science and research that were selected for this fact sheet were used or tested in the MD-DE-DC District from 2001 through 2003, and include established methods, new approaches, and preliminary research. The USGS usually relies on standard methods or protocols when conducting water-resources research. Occasionally, traditional methods must be modified to address difficult environmental questions or challenging sampling conditions. Technologies developed for other purposes can sometimes be successfully applied to the collection or dissemination of water-resources data. The USGS is continually exploring new ways to collect, transmit, evaluate, and interpret data. The following applications of hydrologic science and research illustrate a few of the recent advances made by scientists working for and with the USGS.

Fact Sheet↗

The World Coal Quality Inventory (WoCQI)

The Issue Policymakers around the world require accurate information on coal, particularly information on coal properties and characteristics, to make informed decisions regarding the best use of indigenous resources, international import needs and export opportunities, domestic and foreign policy objectives, technology transfer opportunities, foreign investment prospects, environmental and health assessments, and byproduct use and disposal issues.

Fact Sheet↗