Molecular tools for bathing water assessment in Europe: Balancing social science research with a rapidly developing environmental science evidence-base

The use of molecular tools, principally qPCR, versus traditional culture-based methods for quantifying microbial parameters (e.g., Fecal Indicator Organisms) in bathing waters generates considerable ongoing debate at the science–policy interface. Advances in science have allowed the development and application of molecular biological methods for rapid (~2 h) quantification of microbial pollution in bathing and recreational waters. In contrast, culture-based methods can take between 18 and 96 h for sample processing. Thus, molecular tools offer an opportunity to provide a more meaningful statement of microbial risk to water-users by providing near-real-time information enabling potentially more informed decision-making with regard to water-based activities. However, complementary studies concerning the potential costs and benefits of adopting rapid methods as a regulatory tool are in short supply. We report on findings from an international Working Group that examined the breadth of social impacts, challenges, and research opportunities associated with the application of molecular tools to bathing water regulations.     

Spatiotemporal Variability of Modeled Watershed Scale Surface‐Depression Storage and Runoff for the Conterminous United States

This study explores the viability of using simulated monthly runoff as a proxy for landscape‐scale surface‐depression storage processes simulated by the United States Geological Survey’s National Hydrologic Model (NHM) infrastructure across the conterminous United States (CONUS). Two different temporal resolution model codes (daily and monthly) were run in the NHM with the same spatial discretization. Simulated values of daily surface‐depression storage (treated as a decimal fraction of maximum volume) as computed by the daily Precipitation‐Runoff Modeling System (NHM‐PRMS) and normalized runoff (0 to 1) as computed by the Monthly Water Balance Model (NHM‐MWBM) were aggregated to monthly and annual values for each hydrologic response unit (HRU) in the CONUS geospatial fabric (HRU; n = 109,951) and analyzed using Spearman’s rank correlation test. Correlations between simulated runoff and surface‐depression storage aggregated to monthly and annual values were compared to identify where which time scale had relatively higher correlation values across the CONUS. Results show Spearman’s rank values >0.75 (highly correlated) for the monthly time scale in 28,279 HRUs (53.35%) compared to the annual time scale in 41,655 HRUs (78.58%). The geographic distribution of HRUs with highly correlated monthly values show areas where surface‐depression storage features are known to be common (e.g., Prairie Pothole Region, Florida).     

LogD: lipophilicity for ionisable compounds

The octanol/water partition coefficient (Kow) for organic compounds is widely used in predictive environmental studies. A significant proportion of contaminants of surface and ground water are ionisable (e.g. many pesticides, pharmaceuticals, metabolites). Such compounds may be partially ionised dependent on the pH. Since the neutral and ionic species exhibit different polarities, the Kow value of ionisable pesticides is pH dependent. It is therefore essential to determine Kow values over the full range of pH that occurs in the environment in order to get appropriate predictors. Numerous methods are available to measure lipophilicity but only a few are appropriate for ionisable pesticides (e.g. pH metric and filter probe methods). Parameters such as pH and ionic strength need to be carefully controlled when working with ionisable compounds. Variation of these factors probably explains why literature can yield Kow values that differ by more than one order of magnitude for some compounds. In this article, Kow values obtained for six acidic pesticides with three different methods are compared as well (data from the literature, measured by pH metric method and calculated with five computer programs). The values used in predictive regression equations needs to be either measured with a suitable method or selected from the literature with great care.     

Spatial distribution and concentration of sulfur in relation to vegetation cover and soil properties on a reclaimed sulfur mine site (Southern Poland)

This work aims to assess the spatial distribution and concentration of sulfur in the topsoil layer and to determine the relationships between sulfur concentration, soil pH, soil electrical conductivity, and plant cover at the reforested site of the former sulfur mine (Southern Poland). Soil samples were collected from 0 to 20 cm (topsoil) from a total of 86 sampling points in a regular square grid with sides of 150 m. Plant cover was assayed in circular plots with an area of 100 m², divided into a woody plant layer and herbaceous plant layer. Soil properties such as particle size distribution, pH in KCl and H₂O, soil electrical conductivity (EC), soil organic carbon (SOC), total nitrogen (N_T), and total sulfur (S_T) were determined. The degree of soil contamination with sulfur was assessed based on the guidelines of the Institute of Soil Science and Plant Cultivation (IUNG), Poland. The results indicate that remediation and application of lime were not fully effective in spatial variation, because 33 points with sulfur contamination above 500 mg kg^?1 were observed. These spots occurred irregularly in the topsoil horizons. This high sulfur concentration in the soil did not result in severe acidification (below 4.5) in all cases, most likely due to neutralization from the application of high doses of flotation lime. High vegetative cover occurred at some points with high soil sulfur concentrations, with two points having S concentration above 40,000 mg kg^?1 and tree cover about 60%. Numerous points with high soil EC above 1500 μS cm^?1 as well as limited vegetation and high soil sulfur concentrations, however, indicate that the reclamation to forest is still not completely successful.     

Predicting System-Scale Impacts of Oyster Clearance on Phytoplankton Productivity in a Small Subtropical Estuary

Oyster populations in south Florida estuaries have declined in part through altered salinity driven by anthropogenic changes in freshwater inputs. In particular, the St. Lucie Estuary (SLE) in southeastern Florida has suffered widespread loss of oyster habitat. With efforts underway to improve water quality and oyster habitat in the SLE, the goal of this study was to develop a model to assess ecosystem level impacts of oyster restoration. Phytoplankton and oyster biomass modeling targets were established from observational data collected from 2005 to 2009. Modeled oyster biomass production and filtration fluctuated with temperature, salinity, and total suspended solids from a combination of observational and predicted input functions in 10-year simulations (1998–2007). Model estimates of oyster biomass fluctuated with salinity from near zero after extreme freshwater discharge in 2002–2003 and 2004–2005 to maximum values near 150.0 and 200.0 g?C?m^?2 in spring 1999 and fall 2006. There was potential for algal blooms as turnover time for the phytoplankton standing stock (15.6 days) was faster than water mass turnover (21.0 days). While >1,000 days were required for 50 ha of oyster habitat to filter the entire volume of the estuarine segment, filter time reduced to <20 days with an estimated fivefold increase in net consumption of phytoplankton if the oyster habitat was increased to 300 ha. Re-establishment of biologically desirable salinity envelopes would stabilize oyster survival allowing the possibility for successful habitat restoration to benefit water quality and faunal attributes of the St. Lucie Estuary.     

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

Hydrologic Controls on Nitrogen and Phosphorous Dynamics in Relict Oxbow Wetlands Adjacent to an Urban Restored Stream

Although wetlands are known to be sinks for nitrogen (N) and phosphorus (P), their function in urban watersheds remains unclear. We analyzed water and nitrate (NO₃^?) and phosphate (PO₄^3?) dynamics during precipitation events in two oxbow wetlands that were created during geomorphic stream restoration in Baltimore County, Maryland that varied in the nature and extent of connectivity to the adjacent stream. Oxbow 1 (Ox1) received 1.6‐4.2% and Oxbow 2 (Ox2) received 4.2‐7.4% of cumulative streamflow during storm events from subsurface seepage (Ox1) and surface flow (Ox2). The retention time of incoming stormwater ranged from 0.2 to 6.7 days in Ox1 and 1.8 to 4.3 days in Ox2. Retention rates in the wetlands ranged from 0.25 to 2.74 g N/m²/day in Ox1 and 0.29 to 1.94 g N/m²/day in Ox2. Percent retention of the NO₃^?‐N load that entered the wetlands during the storm events ranged from 64 to 87% and 23 to 26%, in Ox1 and Ox2, respectively. During all four storm events, Ox1 and Ox2 were a small net source of dissolved PO₄^3? to the adjacent stream (i.e., more P exited than entered the wetland), releasing P at a rate of 0.23‐20.83 mg P/m²/day and 3.43‐24.84 mg P/m²/day, respectively. N and P removal efficiency of the oxbows were regulated by hydrologic connectivity, hydraulic loading, and retention time. Incidental oxbow wetlands have potential to receive urban stream and storm flow and to be significant N sinks, but they may be sources of P in urban watersheds.     

Analysis and comparison of inertinite-derived adsorbent with conventional adsorbents

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples. In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 degrees C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4 x 6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated carbons. Implications: The United States currently imports two-thirds of its crude oil, leaving its transportation system especially vulnerable to disruptions in international crude supplies. UT Arlington has developed a liquefaction process that converts coal, abundant in the United States, to crude oil. This work demonstrated that the undissolvable solid coal residual from the liquefaction process, called inertinite, can be converted to an activated carbon adsorbent. Although its surface area and adsorption capacity are not as high as those for commercially available carbons, the inertinite source material would be available at no cost, and its beneficial reuse would avoid the need for disposal.     

Crushed concrete as a phosphate binding material: a potential new management tool

To avoid eutrophication of receiving waters, effective methods to remove P in urban and agricultural runoff are needed. Crushed concrete may be an effective filter material to remove dissolved and particulate P. Five types of crushed concrete were tested in the laboratory to evaluate the retention capacity of dissolved P. All types removed P very effectively (5.1-19.6 g P kg(-1) concrete), while the possible release of bound P varied between 0.4 and 4.6%. The retention rate was positively related to a decreasing concrete grain size due to an increasing surface area for binding. The P retention was also related to a marked increase in pH (up to pH 12), and the highest retention was observed when pH was high. Under these circumstances, column experiments showed outlet P concentrations <0.0075 mg P L(-1). Furthermore, experiments revealed that release of heavy metals is of no importance for the treated water. We demonstrate that crushed concrete can be an effective tool to remove P in urban and agricultural runoff as filter material in sedimentation/infiltration ponds provided that pH in the treated water is neutralized or the water is diluted before outlet to avoid undesired effects caused by the high pH.