Formation of Targeted and Novel Disinfection Byproducts during Chlorine Photolysis in the Presence of Bromide.

Chlorine photolysis is an advanced oxidation process that relies on the combination of direct chlorination by free available chlorine, direct photolysis, and reactive oxidants to transform contaminants. In waters that contain bromide, free available bromine and reactive bromine species can also form. However, little is known about the underlying mechanisms or formation potential of disinfection byproducts (DBPs) under these conditions. We investigated reactive oxidant generation and DBP formation under dark conditions, chlorine photolysis, and radical-quenched chorine photolysis with variable chlorine (0-10 mg-Cl2/L) and bromide (0-2,000 µg/L) concentrations, as well as with free available bromine. Probe loss rates and ozone concentrations increase with chlorine concentration and are minimally impacted by bromide. Radical-mediated processes partially contribute to the formation targeted DBPs (i.e., trihalomethanes, haloacetic acids, haloacetonitriles, chlorate, and bromate), which increase with increasing chlorine concentration. Chlorinated novel DBPs detected by high-resolution mass spectrometry are attributable to a combination of dark chlorination, direct halogenation by reactive chlorine species, and transformation of precursors, whereas novel brominated DBPs are primarily attributable to dark bromination of electron-rich formulas. The formation of targeted and novel DBPs during chlorine photolysis in waters with elevated bromide may limit treatment applications.

Bromide occurrence in Croatian groundwater and application of literature models for bromate formation.

Bromide in water can form undesirable by-products such as bromate when treated by ozonation during drinking water production. The maximum contaminant level (MCL) for bromate is 10 µg/L in most countries because it is suspected of being carcinogenic. In this paper, the geographical distribution of bromide concentration in Croatian groundwater is presented covering the Pannonian basin and the Dinarides (Adriatic Sea). Groundwater in Croatian wellfields predominantly has a bromide content of less than 50 µg/L and thus belongs to the group with low potential for bromate formation. Waters with higher bromide concentrations were found mainly in the coastal regions of Croatia, probably due to seawater intrusion. In addition, bromide concentration showed a positive correlation of 0.6 with conductivity, chloride, and sodium. In addition, the potential of 123 groundwaters analyzed in this study to form bromate when treated with ozone was evaluated using models available in the literature. Analysis of water from Croatian wellfields indicated that the potential for bromate formation above the MCL during ozonation was relatively low. The models used from the literature predicted quite different values of bromate concentration when applied to the same water, with some values exceeding those theoretically possible. Selected models may be useful as a general warning of possible bromate formation.

Trace Analysis of 61 Emerging Br-, Cl-, and I-DBPs: New Methods to Achieve Part-Per-Trillion Quantification in Drinking Water.

Disinfection byproducts (DBPs) are a ubiquitous source of chemical exposure in drinking water and have been associated with serious health impacts in human epidemiologic studies. While toxicology studies have pinpointed DBPs with the greatest toxic potency, analytical methods have been lacking for quantifying complete classes of most toxic DBPs at sufficiently low quantification limits (ng/L). This new method reports the parts-per-trillion quantification for 61 toxicologically significant DBPs from 7 different chemical classes, including unregulated iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes, haloketones, haloacetonitriles, halonitromethanes, and haloacetamides, in addition to regulated HAAs and THMs. The final optimized method uses salt-assisted liquid-liquid extraction in a single extraction method for a wide range of DBPs, producing the lowest method detection limits to-date for many compounds, including highly toxic iodinated, brominated, and nitrogen-containing DBPs. Extracts were divided for the analysis of the HAAs (including iodinated HAAs) by diazomethane derivatization and analysis using a GC-triple quadrupole mass spectrometer with multiple reaction monitoring, resulting in higher signal-to-noise ratios, greater selectivity, and improved detection of these compounds. The remaining DBPs were analyzed using a GC-single quadrupole mass spectrometer with selected ion monitoring, utilizing a multimode inlet allowed for lower injection temperatures to allow the analysis of thermally labile DBPs. Finally, the use of a specialty-phase GC column (Restek Rtx-200) significantly improved peak shapes, which improved separations and lowered detection limits. Method detection limits for most DBPs were between 15 and 100 ng/L, and relative standard deviations in tap water samples were mostly between 0.2 and 30%. DBP concentrations in real samples ranged from 40 to 17 760 ng/L for this study.

Disinfection byproducts and halogen-specific total organic halogen speciation in chlorinated source waters - The impact of iopamidol and bromide.

This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts (DBPs) upon chlorination of natural organic matter (NOM) in the presence of iopamidol and bromide (Br-). Experiments were conducted with low bromide source waters with different NOM characteristics from Northeast Ohio, USA and varied spiked levels of bromide (2-30 µmol/L) and iopamidol (1-5 µmol/L). Iopamidol was found to be a direct precursor to trihalomethane (THM) and haloacetic acid formation, and in the presence of Br- favored brominated analogs. The concentration and speciation of DBPs formed were impacted by iopamidol and bromide concentrations, as well as the presence of NOM. As iopamidol increased the concentration of iodinated DBPs (iodo-DBPs) and THMs increased. However, as Br- concentrations increased, the concentrations of non-brominated iodo- and chloro-DBPs decreased while brominated-DBPs increased. Regardless of the concentration of either iopamidol or bromide, bromochloroiodomethane (CHBrClI) was the most predominant iodo-DBP formed except at the lowest bromide concentration studied. At relevant concentrations of iopamidol (1 µmol/L) and bromide (2 µmol/L), significant quantities of highly toxic iodinated and brominated DBPs were formed. However, the rapid oxidation and incorporation of bromide appear to inhibit iodo-DBP formation under conditions relevant to drinking water treatment.

Electrochemical Umpolung of Bromide: Transition-Metal-Free Bromination of Indole C⁻H Bond.

A facile and sustainable electrochemical umpolung of bromide ion protocol was developed under mild reaction conditions. Transition metal catalysts and exogenous chemical oxidants were obviated for the bromination of C⁻H bond. Notably, graphite rod, which is commercially available at supermarkets and is inexpensive, was employed as the electrode material. This operationally easy and environmentally friendly approach accomplished the synthesis of 3-bromoindole in excellent yield and regioselectivity.

Risk associated with increasing bromide in drinking water sources in Yancheng City, China.

The bromide concentration in water source (WS) of Yancheng City in China increased unexpectedly due to industrial discharge and saltwater intrusion, which leads to the formation of trihalomethane (THMs) in finished water of water treatment plants (WTP), especially brominated THMs. In Yancheng City, drinking water is supplied by WTP1 and WTP2, primarily sourced by WS1 and WS2, respectively. In this paper, the seasonal variations of bromide in WS1 and WS2 and THMs species in WTP1 and WTP2 were analyzed and compared. The effects of bromide in WS on THMs formation in finished water of WTP in terms of bromine substitution factor (BSF) were simulated by statistical linear model. Although the THMs concentrations in WTP1 were approximate to that in WTP2, the brominated THMs concentrations in WTP1 were higher than that in WTP2 due to higher bromide concentration in WS1 than WS2. The cancer risk analysis indicated that THMs' species of DBCM is the dominant THMs for WTP1 as well as WTP2, which can provide more information for WTPs with higher bromide concentration in water source.

Chemical application strategies to protect water quality.

Management of turfgrass on golf courses and athletic fields often involves application of plant protection products to maintain or enhance turfgrass health and performance. However, the transport of fertilizer and pesticides with runoff to adjacent surface waters can enhance algal blooms, promote eutrophication and may have negative impacts on sensitive aquatic organisms and ecosystems. Thus, we evaluated the effectiveness of chemical application setbacks to reduce the off-site transport of chemicals with storm runoff. Experiments with water soluble tracer compounds confirmed an increase in application setback distance resulted in a significant increase in the volume of runoff measured before first off-site chemical detection, as well as a significant reduction in the total percentage of applied chemical transported with the storm runoff. For example, implementation of a 6.1 m application setback reduced the total percentage of an applied water soluble tracer by 43%, from 18.5% of applied to 10.5% of applied. Evaluation of chemographs revealed the efficacy of application setbacks could be observed with storms resulting in lesser (e.g. 100 L) and greater (e.g. > 300 L) quantities of runoff. Application setbacks offer turfgrass managers a mitigation approach that requires no additional resources or time inputs and may serve as an alternative practice when buffers are less appropriate for land management objectives or site conditions. Characterizing potential contamination of surface waters and developing strategies to safeguard water quality will help protect the environment and improve water resource security. This information is useful to grounds superintendents for designing chemical application strategies to maximize environmental stewardship. The data will also be useful to scientists and regulators working with chemical transport and risk models.

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes.

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW <1kDa and fraction with MW 3-10kDa, and the DBP's generation ability of lower molecular weight DOM (<10kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.

Formation and control of nitrogenous DBPs from Western Australian source waters: Investigating the impacts of high nitrogen and bromide concentrations.

We studied the formation of four nitrogenous DBPs (N-DBPs) classes (haloacetonitriles, halonitromethanes, haloacetamides, and N-nitrosamines), as well as trihalomethanes and total organic halogen (TOX), after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone-biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection.

Disinfection byproduct regulatory compliance surrogates and bromide-associated risk.

Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations.

Colloid Mobilization in a Fractured Soil: Effect of Pore-Water Exchange between Preferential Flow Paths and Soil Matrix.

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

Arsenic in Groundwater: The Deep Late Pleistocene Aquifers of the Western Bengal Basin.

in groundwaters from 145 wells across central West Bengal, India, those from Pleistocene aquifers at depths >70 m beneath paleo-interfluves contain <10 µg/L As. Pleistocene aquifers beneath deep paleo-channels typically host groundwaters containing 10-100 µg/L As at depths between 120 and 180 m. The depth profiles of As and SO4 and the conservative tracers Cl/Br, δ(18)O, and δ(2)H show that the As in Pleistocene groundwater beneath deep paleo-channels is relict and does not arise from migration downward of As-polluted groundwater in overlying aquifers. We postulate that the As was liberated in situ by reduction of minimal iron oxyhydroxides in the gray Pleistocene sands by organic matter infiltrating from riverbeds during late Pleistocene or earliest Holocene times. Mitigation of the widespread As-pollution in shallow aquifers through exploitation of deep Pleistocene aquifers would improve if guided by an understanding of the distribution of buried paleo-channels and paleo-interfluves and the knowledge that As may be present naturally in groundwater at depths >150 m beneath deep paleo-channels.

Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO.

Previous studies showed that significant bromate (BrO3(-)) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3(-) and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3(-) formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tricarboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3(-) formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L(-1)) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3(-), total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.

Iodide, bromide, and ammonium in hydraulic fracturing and oil and gas wastewaters: environmental implications.

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

Effect of Sediment Gas Voids and Ebullition on Benthic Solute Exchange.

The presence of free gas in sediments and ebullition events can enhance the pore water transport and solute exchange across the sediment-water interface. However, we experimentally and theoretically document that the presence of free gas in sediments can counteract this enhancement effect. The apparent diffusivities (Da) of Rhodamine WT and bromide in sediments containing 8-18% gas (Da,YE) were suppressed by 7-39% compared to the control (no gas) sediments (Da,C). The measured ratios of Da,YE:Da,C were well within the range of ratios predicted by a theoretical soil model for gas-bearing soils. Whereas gas voids in sediments reduce the Da for soluble species, they represent a shortcut for low-soluble species such as methane and oxygen. Therefore, the presence of even minor amounts of gas can increase the fluxes of low-soluble species (i.e., gases) by several factors, while simultaneously suppressing fluxes of dissolved species.

A Comprehensive Analysis of Groundwater Quality in The Barnett Shale Region.

The exploration of unconventional shale energy reserves and the extensive use of hydraulic fracturing during well stimulation have raised concerns about the potential effects of unconventional oil and gas extraction (UOG) on the environment. Most accounts of groundwater contamination have focused primarily on the compositional analysis of dissolved gases to address whether UOG activities have had deleterious effects on overlying aquifers. Here, we present an analysis of 550 groundwater samples collected from private and public supply water wells drawing from aquifers overlying the Barnett shale formation of Texas. We detected multiple volatile organic carbon compounds throughout the region, including various alcohols, the BTEX family of compounds, and several chlorinated compounds. These data do not necessarily identify UOG activities as the source of contamination; however, they do provide a strong impetus for further monitoring and analysis of groundwater quality in this region as many of the compounds we detected are known to be associated with UOG techniques.

Factors affecting trihalomethane formation and speciation during chlorination of reclaimed water.

A hybrid process with membrane bioreactor (MBR) and powdered activated carbon (PAC), PAC/MBR, was used for real municipal wastewater treatment and reuse. The roles of chlorine dose, contact time, pH and bromide in trihalomethane (THM) formation and speciation during chlorination of the reclaimed water were investigated. Total trihalomethane (TTHM) yield exponentially increased to maximum with increasing chlorine dose (correlation coefficient R2=0.98). Prolonging substrate chlorine contact time significantly promoted TTHM formation. Less than 40% of THMs formed in the first 24 h, indicating that the PAC/MBR effluent organic matters were mostly composed of slow-reacting precursors. Increasing pH and bromide concentration facilitated THM formation. Higher chlorine dose and contact time enhanced chloro-THM formation. The bromo-THM formation was favored at near neutral condition. Despite the variation of chlorine dose, contact time and pH, the yield of THM species in order was usually CHCl3>CHBrCl2>CHBr2Cl>CHBr3. However, THM speciation shifted from chlorinated species to brominated species with increasing bromide concentration.

Boiling of simulated tap water: effect on polar brominated disinfection byproducts, halogen speciation, and cytotoxicity.

Tap water typically contains numerous halogenated disinfection byproducts (DBPs) as a result of disinfection, especially of chlorination. Among halogenated DBPs, brominated ones are generally significantly more toxic than their chlorinated analogues. In this study, with the aid of ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 79/81, whole spectra of polar brominated DBPs in simulated tap water samples without and with boiling were revealed. Most polar brominated DBPs were thermally unstable and their levels were substantially reduced after boiling via decarboxylation or hydrolysis; the levels of a few aromatic brominated DBPs increased after boiling through decarboxylation of their precursors. A novel adsorption unit for volatile total organic halogen was designed, which enabled the evaluation of halogen speciation and mass balances in the simulated tap water samples during boiling. After boiling for 5 min, the overall level of brominated DBPs was reduced by 62.8%, of which 39.8% was volatilized and 23.0% was converted to bromide; the overall level of chlorinated DBPs was reduced by 61.1%, of which 44.4% was volatilized and 16.7% was converted to chloride; the overall level of halogenated DBPs was reduced by 62.3%. The simulated tap water sample without boiling was cytotoxic in a chronic (72 h) exposure to mammalian cells; this cytotoxicity was reduced by 76.9% after boiling for 5 min. The reduction in cytotoxicity corresponded with the reduction in overall halogenated DBPs. Thus, boiling of tap water can be regarded as a "detoxification" process and may reduce human exposure to halogenated DBPs through tap water ingestion.

Production and characterization of polypropylene composites filled with glass fibre recycled from pyrolysed waste printed circuit boards.

Waste printed circuit boards (WPCBs) are composed of nearly 70% non-metals, which are generally recycled as low-value filling materials or even directly dumped in landfills. In this study, polypropylene (PP) composites reinforced by recycled pure glass fibres (RGF) from pyrolysed WPCBs were successfully produced. The manufacturing process, mechanical properties and thermal behaviour of the composites were investigated. The results showed that the appropriate addition of RGF in the composites can significantly improve the mechanical properties and thermal behaviour. When the added content of RGF was 30%, the maximum increment of tensile strength, impact strength, flexural strength and flexural modulus of the glass fibre (GF)/PP composites are 25.93%, 41.38%, 31.16% and 68.42%, respectively, and the vicat softening temperature could rise by 4.6°C. Furthermore, leaching of the GF/PP composites was also investigated. The GF/PP composites exhibited high performance and non-toxicity, offering a promising method to recycle RGF from pyrolysed WPCBs with high-value applications.

Impact of halides on the photoproduction of reactive intermediates from organic matter.

The excitation of dissolved organic matter (DOM) from sunlight produces a range of reactive intermediates, including triplet-excited state dissolved organic matter ((3)DOM*), hydroxyl radical (HO(•)), and singlet oxygen ((1)O2). These intermediates are important for the inactivation of pathogens and for the degradation of trace organic contaminants (OC) within natural and engineered systems. However, halides found in the background matrix can alter the photoproduction rates by promoting or quenching the formation of these intermediates. Apparent quantum yields (Φ(a)) for (1)O2, HO(•), and steady state (3)DOM* concentrations photoproduced from DOM isolates were determined with varying concentrations of chloride and bromide. Fluorescence quantum yields were measured as well to probe the photophysics of the system. The maximum fluorescence quantum yield (ΦF) decreased with the addition of halides, representing a quenching of the excited singlet state of DOM. In contrast, the steady state concentrations for (3)DOM* were enhanced, suggesting intersystem crossing from the singlet state to the triplet state was increased by the presence of halides. The Φ(a) for (1)O2 was increased with the addition of halides, which was expected following the (3)DOM* results because the mechanism for (1)O2 production occurs through the inactivation of (3)DOM* by dissolved oxygen. Although HO(•) production would be expected to follow (1)O2, the opposite trend was seen, which suggests the formation of HO(•) does not occur through the same precursor. Understanding the impact of specific quenchers on DOM could be a key to understanding the true formation potential for reactive intermediates and is especially important in estuaries and wastewater impacted aquatic systems.