Towards a classification of organic enrichment in marine sediments based on biogeochemical indicators

A nomogram is developed to show that pH, redox potentials (Eh_NHE) and measures of dissolved sulfides (H₂S + HS⁻ + S²⁻)(total free S²⁻) can be used to classify organic enrichment impacts in marine sediments. The biogeochemical cycle of sulfur in marine sediments is described to show that changes in macrobenthic infauna community structure associated with high levels of organic matter supply result from stress due to oxygen deficiency (hypoxia and anoxia) and toxic effects of S²⁻. The changes reflect enhancement of microbial sulfate reduction under conditions of high organic matter sedimentation and the progressive formation of hypoxic–anoxic conditions measured by decreased Eh_NHE and increased concentrations of S²⁻. The nomogram provides a basis for classification of the oxic status of marine sediments based on changes in inter-related biological and biogeochemical variables along an organic enrichment gradient.     

Organochlorine micropollutants in the Jiulong River Estuary and Western Xiamen Sea, China

Organochlorine contaminants including 12 polychlorinated biphenyl (PCB) congeners and 18 insecticides were determined in water, pore water and sediments of the Jiulong River Estuary and Western Xiamen Sea, China. The results showed that the levels of the total PCBs ranged from non-detectable to 1500 ng l⁻¹ in water, from 209 to 3870 ng l⁻¹ in pore water, and from 2.78 to 14.8 ng g⁻¹ dry weight in sediments. Total organochlorine insecticide concentrations were from below the limit of detection to 2480 ng l⁻¹ in water, from 267 to 33400 ng l⁻¹ in pore water, and from 4.22 to 46.3 ng g⁻¹ dry weight in sediments. Concentrations of PCBs and insecticides in pore water were significantly higher than those in surface water, due to the high affinity of these hydrophobic compounds for sediment phase. The PCB congeners with the highest concentrations were CB153, CB180 and CB194, which together accounted for 68–87% of total PCBs in water, pore water and sediment. Among the hexachlorocyclohexane (HCH) compounds, beta-HCH was found to be a major isomer. Analysis of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane (DDT) and its metabolites showed that 1,1-dichloro-2[o-chlorophenyl]-2[p-chlorophenyl]-ethylene (DDE) was dominant in the group. In comparison to a 1998 study in the Western Xiamen Sea, levels of organochlorines were enhanced due probably to recent inputs and changes in sediments.     

An overview of toxicant identification in sediments and dredged materials

The identification of toxicants affecting aquatic benthic systems is critical to sound assessment and management of our nation's waterways. Identification of toxicants can be useful in designing effective sediment remediation plans and reasonable options for sediment disposal. Knowledge of which contaminants affect benthic systems allows managers to link pollution to specific dischargers and prevent further release of toxicant(s). In addition, identification of major causes of toxicity in sediments may guide programs such as those developing environmental sediment guidelines and registering pesticides, while knowledge of the causes of toxicity which drive ecological changes such as shifts in benthic community structure would be useful in performing ecological risk assessments. To this end, the US Environmental Protection Agency has developed tools (toxicity identification and evaluation (TIE) methods) that allow investigators to characterize and identify chemicals causing acute toxicity in sediments and dredged materials. To date, most sediment TIEs have been performed on interstitial waters. Preliminary evidence from the use of interstitial water TIEs reveals certain patterns in causes of sediment toxicity. First, among all sediments tested, there is no one predominant cause of toxicity; metals, organics, and ammonia play approximately equal roles in causing toxicity. Second, within a single sediment there are multiple causes of toxicity detected; not just one chemical class is active. Third, the role of ammonia is very prominent in these interstitial waters. Finally, if sediments are divided into marine or freshwater, TIEs perforMed on interstitial waters from freshwater sediments indicate a variety of toxicants in fairly equal proportions, while TIEs performed on interstitial waters from marine sediments have identified only ammonia and organics as toxicants, with metals playing a minor role. Preliminary evidence from whole sediment TIEs indicates that organic compounds play a major role in the toxicity of marine sediments, with almost no evidence for either metal or ammonia toxicity. However, interpretation of these results may be skewed because only a small number of interstitial water (n = 13) and whole sediment (n = 5) TIEs have been completed. These trends may change as more data are collected.     

Pesticides in Sediments From Queensland Irrigation Channels and Drains

Pesticide concentration in sediment from irrigation areas can provide information required to assess exposure and fate of these chemicals in freshwater ecosystems and their likely impacts to the marine environment. In this study, 103 sediment samples collected from irrigation channels and drains in 11 agricultural areas of Queensland were analysed for a series of past and presently used pesticides including various organochlorines, synthetic pyrethroids, benzoyl ureas, triazines and organophosphates. The most often detected compounds were endosulphans (, β and/or endosulphan sulphate) which were detectable in 78 of the 103 samples and levels ranged from below the limit of quantification (0.1 ng g⁻¹ dw) up to 840 ng g⁻¹ dw. DDT and its metabolites were the second most often detected pesticide investigated (74 of the 103 samples) with concentrations up to 240 ng g⁻¹ dw of ∑DDTs. Mean ∑endosulphan and ∑DDT concentrations were 1–2 orders of magnitude higher in sediments from the irrigation areas which are dominated by cotton cultivation compared to those which are dominated by sugarcane cultivation. In contrast to these insecticides, the herbicides diuron, atrazine and ametryn were the compounds which were most often detected in sediments from irrigation drains in sugarcane areas with maximum concentrations in areas of 120, 70 and 130 ng g⁻¹ dw, respectively. In particular during flood events, when light is limiting, transport of these photosynthesis inhibiting herbicides from the sugarcane cultivation areas to the marine environment may result in additional stress of marine plants.     

A Case Study on Identifying the Toxicant in Effluent Discharged from a Chemical Plant

Three phase procedures of toxicity identification evaluation (TIE) were conducted using Daphnia magna to identify the toxicant in effluent discharged from a chemical plant in Nanjing. Phase I toxicity characterization procedures suggested nonpolar organic compounds were responsible for the whole effluent toxicity. In phase II toxicity identification procedures, the effluent toxicity was recovered by C₁₈ solid-phase extraction and concentration steps. Gas chromatography–mass spectrometry (GC/MS) of the concentrate indicated that benzopyrone and phenol were present in the effluent at sufficient concentrations to cause the effluent toxicity. In phase III toxicity confirmation procedures, benzopyrone and phenol mixture tests and mass balance determinations with toxic units (TU) confirmed these compounds were the key toxicants accounting for 44.6% and 32.9% of the whole effluent toxicity, respectively.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

Dynamics of Microbiological Contamination at a Marine Recreational Site

Levels of bacterial indicators of pollution are related with marine salinity and turbidity at both high tide (HT) and low tide (LT). The salinity varied from values around 26.9 ppm at the LT and 28.6 ppm at the high tide but affected total and faecal coliform (FC) estimates. Salinity readings of 25–30 ppm produced microbial counts below 10⁻² MPN/100 ml total coliforms (TCs) whereas salinity of 15–22 ppm produced a TC level of 4.6×10⁻⁴ MPN/100 ml. Turbidity peaks in the samples are accompanied by peaks of microbial contamination of the seawater indicating that the contamination is normally deposited at the marine sediment rather than in the water column. In fact, samples collected under heavy stormy weather, in which the water agitation resulted in turbidity values up to 68.3 NTU, produced maximum microbial counts.     

A toxicity identification evaluation of silty marine harbor sediments to characterize persistent and non-persistent constituents

Sediment toxicity in silty marine harbor sediments is frequently dominated by ammonia or sulfide, leaving the adverse effects of persistent toxic substances unnoticed. To investigate the latter, we subjected interstitial water from three contaminated silty sediments to toxicity identification evaluation (TIE) phase I manipulations and tested for toxicity with four bioassays: the amphipod Corophium volutator (survival as an endpoint), the sea urchin Psammechinus miliaris (fertilization, embryo development) and the bacterium Vibrio fischeri (bioluminescence inhibition).The graduated pH manipulations identified the prominent toxicity of ammonia in the amphipod and sea urchin embryo tests, and also sulfide toxicity in the bacterium test. In two of the three samples tested with the amphipods, sea urchin embryos and bacteria, a small but significant reduction in interstitial water toxicity was achieved by removing persistent compounds through C(18) solid phase extraction. EDTA chelation resulted in a slight detoxification of the interstitial water for the amphipods and sea urchin embryos, but this was not related to any measured trace metals. Despite the presence of toxic levels of ammonia and sulfide in the harbor sediments, we established the adverse biological effects of persistent constituents by means of the TIE manipulations and in vivo interstitial water bioassays.     

Mesocosm experiments for evaluating the biological efficacy of ozone treatment of marine ballast water

Ballast water is a major pathway for the transfer of non-indigenous species in aquatic environments. The objectives of this study were to determine the ability of ozone to reduce the numbers of a spectrum of marine organisms collected from Puget Sound, Washington in replicated mesocosm (280 l) experiments, and estimate the minimum ozone concentrations as measured by total residual oxidant (TRO) required to reduce organism densities. Ozone treatment was effective in removing bacteria, phytoplankton, and mesozooplankton with initial TRO concentrations of 2–5 mg l⁻¹ as Br₂. Persistence of TRO resulted in an extended period of toxicity and cumulative mortality. TRO decay allowed bacteria populations to multiply when TRO levels fell below 0.5–1.0 mg l⁻¹ as Br₂. Phytoplankton chlorophyll a concentrations were rapidly reduced by ozone treatment and did not increase in any treatments or controls because of lack of light. Overall mesozooplankton viability was rapidly reduced by 90–99% in treatment TRO levels above 1.85 mg l⁻¹ as Br₂. Our study outlines novel protocols that can be used for testing different potential ballast water treatment systems in replicated and controlled mesocosm experiments.     

Attenuation of nitrate in aquitard sediments of southern Ontario

To examine nitrate persistence, detailed geochemical profiling, using core-squeezed water and piezometer samples, was carried out at five sites in southern Ontario where groundwater is moving downward in silt-rich aquitard sediments at rates of 16 to more than 20 cm year⁻¹. Elevated levels of NO₃⁻-N (5–50 mg 1⁻¹) that occur in the shallow groundwater as a result of agricultural activity, were found to be consistently attenuated, generally to very low levels (< 0.05 mg 1⁻¹-N), at the ‘redoxcline’, the horizon marking the boundary between the surficial weathered (brown) sediments and the underlying unweathered (grey) sediments. Tritium dating suggests that groundwater at the redoxcline depths (3–5 m) was recharged between 1970 and 1980, thus the N03 depletion appears to result from biodegradation reactions since no major landuse changes have occurred during this period. The close association of the nitrate depletion zones with the redoxcline, where, in particular, sediment sulphur contents increase abruptly, and where also porewater SO₄²⁻ levels increase, suggests that the dominant attenuation reaction is autotrophic denitrification using reduced sulphur compounds present in the unweathered sediment as the electron donor. Mass balance calculations suggest that the increase in the downward rate of migration of the redoxcline, owing to added sulphur consumption from NO₃⁻ contamination, is only about 1 mm year⁻¹ at these sites. Review of the literature indicates that most silt- and clay-rich sediments have S contents in the same range, or higher, than those investigated here, thus, in most cases where aquifers are overlain by several metres or more of unweathered confining sediments, it is likely that a high degree of protection is afforded from surficial NO₃⁻ contamination.     

Hydrocarbon and coprostanol levels in seawater, sea-ice algae and sediments near Davis station in eastern Antarctica: A regional survey and preliminary results for a field fuel spill experiment

A survey of hydrocarbons and the sterol coprostanol, together with a hydrocarbon degradation experiment, was conducted in a coastal marine environment in East Antarctica. Aliphatic hydrocarbon levels in sea-ice algae were 1.9–12.5 mg m⁻² and in seawater particulate matter 0.07–0.17 μg l⁻¹. Sea-ice algae contained the diatom biomarker, the highly branched isoprenoid (ip) diene ipC_25:2, and Southern Ocean seawater particulate matter samples were distinguished from near shore samples by the presence of nC_21:6. Sea-ice algae and seawater particulate matter samples showed a predominance of even chain n-alkanes. Hydrocarbon levels in sediment samples from anoxic fjord basins were high (45–48 μg g⁻¹) compared to a sub-tidal marine sample (0.7 μg g⁻¹), and were predominantly of bacterial origin. Contaminants detected were linear alkyl benzenes in sewage effluent from Davis station, and polycyclic aromatic hydrocarbons (PAH) which were present in very low levels (parts per trillion) throughout the environment. High levels of 2,6-dimethylnaphthalene were found in anoxic sediment from Ellis Fjord and may arise from a novel bacterial source. Coprostanol concentrations in sediments ranged from 67 to 1280 ng g⁻¹. A dual origin is proposed from marine mammalian faeces and, at several sites, from conversion of algal-derived sterols by anaerobic bacteria. Future studies examining the impact of human sewage from scientific bases or other ventures should use care in interpreting results when such high baseline values, from marine mammalian input, may occur naturally around the Antarctic coast. The potential exists, however, for the technique to distinguish between human and mammalian inputs through measurement of the coprostanol to epicoprostanol ratio, particularly if undertaken with appropriate comparative sampling. Results for a hydrocarbon degradation experiment where a light fuel was applied to an Antarctic beach, showed loss of up to 99% of the fuel within 2 months, mainly by volatilization.     

Glacier hydrochemistry, solute provenance, and chemical denudation at a surge-type glacier in Kuannersuit Kuussuat, Disko Island, West Greenland

In 1995–1998, Han 11 km terrestrial surge of Kuannersuit Glacier, an outlet glacier of the largest ice cap on Disko Island, West Greenland, affected the catchment dramatically. In order to estimate solute fluxes and provenances, bulk meltwaters were sampled at the main subglacial outlet during the initial part of the quiescent phase. The hydrochemistry is significantly influenced by a subglacial basaltic weathering regime with absence of carbonate minerals. The results show that marine and aerosol derived solutes have minimal contribution to the total ion content, whereas sequestration of atmospheric CO₂ associated with carbonation of Ca-rich feldspar and reactive volcanic glass is more dominant than previously reported from glacierized catchments. Application of a sampling strategy dividing water samples into four groups to determine the content of dissolved HCO₃⁻ and CO₃²⁻ shows that the cationic equivalent weathering rate range is 683–860 Σmeq⁺ m⁻² a⁻¹ and solute flux ranges between 76 and 98 t km⁻² a⁻¹. The crustal denudation rate is estimated to 26 t km⁻² a⁻¹, and the transient CO₂ drawdown amounts to 8500–13700 kg C km⁻² a⁻¹.     

The toxicity of marine sediments in Victoria Harbour, Hong Kong

When the toxicity of marine sediment in Hong Kong was evaluated, it was found that the seven sediments collected within Victoria Harbour were severely contaminated with heavy metals, at concentrations many times higher than those in sediments collected from outside the harbour. The highest metal content was recorded in site VS14 (located near the airport runway and the industrialized area), with copper, zinc, lead and chromium values of 3789, 610, 138 and 601 mg kg⁻¹ dry wt, respectively. This site also had the greatest alkaline phosphatase activities (15 fluorescent intensity unit g⁻¹ wet wt), the largest number of total coliforms (910 CFU g⁻¹ wet wt) and sulphate-reducing bacteria (8.5 × 10⁴ cells g⁻¹ wet wt), implying that site VS14 was also contaminated with organic matter and nutrients. Sediment bioassays, Microtox and algal tests, demonstrated that sediment elutriates obtained from site VS14 were of greatest toxicity. The EC₁₀ value in Microtox tests was 17% elutriate, and the 96-h IC₅₀ values using Skeletonema costatum and Dunaliella tertiolecta were 40 and 79% elutriate, respectively. No toxic effects were found in sediment samples collected from the control site outside Victoria Harbour. Significant correlations were found between the results of the algal toxicity test (using S. costatum) and the coliform count and metal content of the sediments. The Microtox test was less sensitive than the algal bioassay, and no sediment elutriate, even from the site mostly contaminated by heavy metals, caused more than 50% inhibition of the light-emitting activity of the bacteria. In this study, S. costatum (the diatom) provided a more sensitive and reliable test species than D. tertiolecta (the flagellate) in differentiating the toxicity of marine sediments.     

Clam burrowing behaviour: Inhibition by copper-enriched sediment

Burrowing behaviour is adaptive and allows clams to escape predation; yet the effects of potentially toxic metals on such behaviour have not been adequately investigated. In natural marine sediment contaminated with copper the time for littleneck clams (Protothaca staminea) to achieve complete burial was recorded. Above a threshold of 5.8 μg g⁻¹ Cu added to dry sediment, the time for 50% of the clams to burrow (ET₅₀) increased logarithmically with increasing sediment copper concentration according to:

logET₅₀ = 0.15 (CU) - 1.37 (n = 4, r² = 0.98)

where ET₅₀=time in hours for 50% of clams to burrow and Cu=μg g⁻¹ Cu in dry sediment. Previously exposed clams had both a lower threshold to Cu and a longer reburrowing time (ET₅₀). Clams exposed to sediment mixed with Chelex-100®-sorbed copper showed no significant change in burrowing time. Bioassays based on claim burrowing behaviour can measure both bioeffectiveness of sediment-sorbed metals and a sublethal effect with ecological meaning.     

Measurement of soluble reactive phosphorus concentration profiles and fluxes in river-bed sediments using DET gel probes

DET (diffusive equilibrium in thin films) gel probes were used for sampling river-bed sediment porewaters, to characterise in situ soluble reactive phosphorus (SRP) concentration profiles and fluxes. DET probes were deployed in three contrasting rural streams: (1) a headwater ‘pristine’ stream, with minimal P inputs from low intensity grassland and no point sources, (2) an intensively cultivated arable catchment, and (3) a stream subject to high P loadings from sewage effluent and intensive arable farming. The DET results showed highly enriched porewater SRP concentrations of between ca. 400 and 5000 μg-P l⁻¹ in the sewage-impacted stream. In contrast, the arable and pristine streams had porewater SRP concentrations <70 μg-P l⁻¹ and <20 μg-P l⁻¹, respectively. Porewater SRP concentration profiles in both the sewage-impacted and arable-impacted streams showed well-defined vertical structure, indicating internal sources and sinks of SRP within the sediment. However, there was little variability in porewater SRP concentrations in the pristine stream. The DET porewater profiles indicated net diffusion of SRP (a) from the overlying river water into the surface sediment and (b) from subsurface sediment upwards towards the sediment–water interface. A mass balance for the sewage-impacted site showed that the influx of SRP into the surface sediments from the overlying river water was small (ca. 1% of the daily river SRP load). The DET results indicated that, in the arable and sewage-impacted streams, the surface ‘cap’ of fine sediment may play an important role in inhibiting upward movement of SRP from subsurface porewaters into the overlying river water, under steady-state, low-flow conditions.     

Huanghe (Yellow River) and its estuary: Sediment origin, transport and deposition

The upper part of the Huanghe (Yellow River) drainage basin supplies 50–60% of the annual water discharge and only 10% of the total river sediment load, while the middle reaches contribute 30–40% of the water flow and 90% of the annual sediment load, because of severe erosion over the Loess Plateau. Large variations in both annual water discharge and sediment load occur in the Huanghe. Heavy sedimentation in the lower reaches of the channel makes the river bed aggrade several centimetres per year. Of the suspended sediment in the river, 90–95% is deposited in the lower part of the river course and in the coastal shallow water area; less than 5–10% escapes from Laizhou Bay and enters the Central Bohai and/or North Huanghai (Yellow Sea). The active delta complex now propagates seawards at a mean rate of 42 km² year⁻¹.     

The Effect of Copper on the Settlement Success of Larvae from the Scleractinian Coral Acropora tenuis

This study examined the effect of copper on the settlement success of planula larvae of the reef-building coral Acropora tenuis during 1994 and 1996 at Magnetic Island, Great Barrier Reef. Copper concentrations of 2, 10, 20 μg l⁻¹ did not inhibit larval settlement after 48-h exposure. However, copper concentrations of 42 μg l⁻¹ and 81 μg l⁻¹ significantly reduced settlement success of A. tenuis larvae after 48-h exposure compared with controls using normal seawater. At 200 μg l⁻¹ copper, all larvae died. EC₅₀ values for the effect of copper on A. tenuis larval settlement were calculated from the 1996 results using measured copper concentrations. The 48-h EC₅₀ was 35 μg l⁻¹ with an upper and lower 95% confidence limit of 37 μg l⁻¹ and 32 μg l⁻¹, respectively. The 48-h NOEC value for both experiments was 20 μg l⁻¹ copper. These experiments provide some of the first data on sub-lethal effects of trace metals on tropical marine organisms, and demonstrate that relatively low copper concentrations impair or inhibit settlement of coral larvae.     

Toxicity identification in metal plating effluent: implications in establishing effluent discharge limits using bioassays in Korea

Because of complexity and diversity of toxicants in effluent, chemical analysis alone gives very limited information on identifying toxic chemicals to test organisms. Toxicity identification evaluation (TIE) techniques have been widely used to identify toxicants in various samples including industrial wastewater as well as natural waters. In response to new regulation for effluent discharge in Korea, which will be effective from 2011, a necessity of studies emerges that investigates toxicity levels in industrial effluents. This work was a preliminary study examining toxicity levels in effluent from one metal plating factory using Daphnia magna (48 h immobility) and identifying toxicity-causing substances. Toxicity tests showed variability on different sampling occasions and the results of TIE methods indicated that both organic compounds and metals contributed to the observed toxicity in metal plating effluent. Further studies are necessary to help reduce effluent toxicity especially from direct dischargers, who will have to comply with the new regulation.     

Pesticide and Herbicide Residues in Sediments and Seagrasses from the Great Barrier Reef World Heritage Area and Queensland Coast

Pesticides and herbicides including organochlorine compounds have had extensive current and past application by Queensland's intensive coastal agriculture industry as well as for a wide range of domestic, public health and agricultural purposes in urban areas. The persistent nature of these types of compounds together with possible continued illegal use of banned organochlorine compounds raises the potential for continued long-term chronic exposure to plants and animals of the Great Barrier Reef. Sediment and seagrass samples were collected from 16 intertidal and 25 subtidal sampling sites between Torres Strait and Townsville, near Mackay and Gladstone, and in Hervey and Moreton Bays in 1997 and 1998 and analysed for pesticide and herbicide residues. Low levels of atrazine (0.1–0.3 μg kg⁻¹), diuron (0.2–10.1 μg kg⁻¹), lindane (0.08–0.19 μg kg⁻¹), dieldrin (0.05–0.37 μg kg⁻¹), DDT (0.05–0.26 μg kg⁻¹), and DDE (0.05–0.26 μg kg⁻¹) were detected in sediments and/or seagrasses. Contaminants were mainly detected in samples collected along the high rainfall, tropical coast between Townsville and Port Douglas and in Moreton Bay. Of the contaminants detected, the herbicide diuron is of most concern as the concentrations detected have some potential to impact local seagrass communities.     

Toxicity identification in metal plating effluent: Implications in establishing effluent discharge limits using bioassays in Korea

Because of complexity and diversity of toxicants in effluent, chemical analysis alone gives very limited information on identifying toxic chemicals to test organisms. Toxicity identification evaluation (TIE) techniques have been widely used to identify toxicants in various samples including industrial wastewater as well as natural waters. In response to new regulation for effluent discharge in Korea, which will be effective from 2011, a necessity of studies emerges that investigates toxicity levels in industrial effluents. This work was a preliminary study examining toxicity levels in effluent from one metal plating factory using Daphnia magna (48 h immobility) and identifying toxicity-causing substances. Toxicity tests showed variability on different sampling occasions and the results of TIE methods indicated that both organic compounds and metals contributed to the observed toxicity in metal plating effluent. Further studies are necessary to help reduce effluent toxicity especially from direct dischargers, who will have to comply with the new regulation.