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Chemical and toxicologic assessment of organic contaminants in surface water using passive samplers

Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Journal of Environmental Quality↗

The environmental geochemistry of Arsenic – An overview

Arsenic is one of the most prevalent toxic elements in the environment. The toxicity, mobility, and fate of arsenic in the environment are determined by a complex series of controls dependent on mineralogy, chemical speciation, and biological processes. The element was first described by Theophrastus in 300 B.C. and named arsenikon (also arrhenicon; Caley and Richards 1956 ) referring to its “potent” nature, although it was originally considered an alternative form of sulfur ( Boyle and Jonasson 1973 ). Arsenikon is believed to be derived from the earlier Persian, zarnik (online etymology dictionary, http://www.etymonline.com/index.php?term=arsenic ). It was not until the thirteenth century that an alchemist, Albertus Magnus, was able to isolate the element from orpiment, an arsenic sulfide (As 2 S 3 ). The complex chemistry required to do this led to arsenic being considered a “bastard metal” or what we now call a “metalloid,” having properties of both metals and non-metals. As a chemical element, arsenic is widely distributed in nature and can be concentrated in many different ways. In the Earth’s crust, arsenic is concentrated by magmatic and hydrothermal processes and has been used as a “pathfinder” for metallic ore deposits, particularly gold, tin, copper, and tungsten ( Boyle and Jonasson 1973 ; Cohen and Bowell 2014 ). It has for centuries been considered a potent toxin, is a common poison in actual and fictional crimes, and has led to significant impacts on human health in many areas of the world ( Cullen 2008 ; Wharton 2010 ).

Reviews in Mineralogy and Geochemistry↗

Insecticides applied to a nursery colony of little brown bats (Myotis lucifugus): Lethal concentrations in brain tissues

Forty-six Myotis lucifugus were collected in May and June 1974 at a nursery colony in Hillsborough County, New Hampshire, that had been sprayed with DDT and chlordane in August and September 1973. When collected, 27 bats were alive, two were convulsing, and 17 were dead. Brains, carcasses, and milk and masticated insects from stomachs were analyzed for organochlorine insecticides and poly-chlorinated biphenyls (PCB's). Concentrations of chemical residues in brains of surviving bats were compared with those of dead and convulsing bats. These comparisons indicated that DDT was the cause of death. Lethal brain concentrations of DDT in adult females averaged 24.52 parts per million (ppm) and suggested that adult M. lucifugus are approximately twice as sensitive to DDT as are adult laboratory rats and mice. Juvenile bats were about 1.5 times more sensitive than adult bats. Large chemical residues were present in milk. We found a statistically significant relationship between declines in carcass residues in lactating females and uterine regression for six of 10 toxicants. Among juveniles, there were corresponding, significant increases (for nine of 10 toxicants) in carcass levels of residues correlated with increasing age (growth of forearm).

New Hampsire↗

Naturally occurring and experimentally induced castor bean (Ricinus communis) poisoning in ducks

Castor bean ( Ricinus communis ) poisoning accounted for the death of several thousand ducks in the Texas panhandle in the fall and winter months of 1969-1971. Signs of intoxication resembled those of botulism, except for mucoid, blood-tinged excreta. The most common lesions were severe fatty change in the liver, widely distributed internal petechial hemorrhages or ecchymoses, and catarrhal enteritis. Nearly intact castor beans were found in the stomach of one duck during field necropsy. Fragments of seed coat resembling castor bean were found in the stomachs of 10 of 14 ducks examined in the laboratory. Clinical signs and postmortem lesions observed in wild ducks were induced experimentally in mallards ( Anas platyrhynchos ) by force-feeding intact castor beans. Toxicity titrations were erratic, but the LD50 appeared to be between three and four seeds. The mouse toxicity test, used to detect Clostridium botulinum toxin in the blood serum of intoxicated ducks, was negative in every case. Hemagglutination and precipitin tests generally failed to detect castor bean in extracts of excreta or intestinal contents of experimentally intoxicated ducks.

Texas↗

Chemotherapy of hexamitiasis in fish

Heramita salmonis , the causative agent of hexamitiasis in salmonoid fishes, is endemic in most trout and salmon hatcheries throughout North America. The etiologic agent, a protozoan flagellate, ostensibly causes cellular damage in the caecal mucosa of afflicted fishes. It is also believed that heavy infections may interfere with normal growth by direct competition with the host for available nutrients in the intestinal tract. While the role of this supposed pathogen is relatively unclear, its presence in test fishes at this laboratory has caused considerable concern during the conduct of controlled nutritional studies. Although McNeil et al (1941) showed that the incidence of Hexamita infections is widespread, hexamitiasis appears to be commercially important only in turkeys (Almquist and Johnson, 1951) and fish (Davis, 1953). Very little has been reported on the protozoacidal effects of various drugs on the Hexamita infections in fish (Fish and McKernan, 1940; Smith and Quistorff, 1940; and Nelson, 1941). The most widely used chemotherapeutic agents are p-carbamidobenzene arsonic acid (carbarsone) and mild mercurous chloride (calomel). Initial attempts at this laboratory to control the parasite in infected fish populations using these two drugs at the recommended concentrations demonstrated that the former was erratic in effectiveness and the latter was toxic and produced loss in fish weight. The present study, therefore, was undertaken to find more effective therapeutic agents which would be palatable, non-toxic, and still effectively eradicate the protozoan from fish.

Journal of Parasitology↗

Effects of heptachlor-contaminated earthworms on woodcocks

The effects on woodcocks ( Philohela minor ) of eating heptachlor-contaminated earthworms were studied experimentally in a series of feeding trials in Louisiana in the winter of 1960-61. Six of 12 woodcocks fed worms which had been contaminated at an average of 2.86 ppm of heptachlor epoxide died within 35 days; 4 more had died by the fifty-third day, when the other 2 were killed for analysis. Worms from areas in Louisiana treated with 2 pounds of heptachlor per acre often contain more than 3 ppm of heptachlor epoxide. Eleven of 12 woodcocks fed worms contaminated at an average of 0.65 ppm survived the full 60 days of the experiment; one died on the forty-fifth day, apparently from other causes. All 11 untreated birds survived. Survivors were kept on one-quarter rations of untreated worms for 11 days. Two woodcocks, untreated previously, died during this starvation period. Five previously treated died; two were observed in spasms at death, and these contained 5.9 and 7.2 ppm heptachlor epoxide in their tissues, suggesting that the previous contaminated diet may have influenced mortality, even though the difference between two of nine dying and five of nine dying is not statistically significant. Surviving starved birds given an unrestricted supply of treated or untreated worms for 5 days survived and gained weight. Residues accumulated in their tissues in this time approached levels in birds that died of heptachlor poisoning. Residues in tissues of birds with different histories suggested residue loss at a rate of approximately 2.8 percent per day. Toxicant absorption was estimated to be in the approximate range of 16-20 percent. Residues in birds fed worms containing 0.65 ppm heptachlor epoxide were in the same general magnitude as those in field-caught birds, suggesting a similar average contamination of food supply. Weights and weight changes did not differ significantly between untreated birds and those receiving the lower level of toxicant. Among birds on one-quarter rations, the percentage of weight that could be lost without danger seemed to be near 20 percent. Woodcocks ate 18-208 grams of worms per day (average, 121 grams), representing 11-143 percent (average, 77 percent) of their body weights; birds ate contaminated and uncontaminated food in essentially equivalent amounts. Symptoms of heptachlor poisoning differed considerably between birds.

Journal of Wildlife Management↗

Body condition and response to pesticides in woodcocks

Response of woodcocks ( Philohela minor ) to heptachlor dosage was closely related to the physical condition of the birds, as reflected by body weight and by body weight in relation to capture weight: in a series of tests with underweight birds, nearly all woodcocks died at dosage levels well below those at which nearly all the birds in a normal-weight series lived. Heptachlor residues in tissues were determined and their loss with time was estimated. Dieldrin proved more toxic than heptachlor to birds of similar weight. Birds in good weight survived massive doses of DDT; some succumbed to smaller spaced serial doses, but only when these were accompanied by starvation rations. When birds were placed in foil-lined boxes after doses of heptachlor added to butter oil or corn oil, it became evident that they passed quantities of oil in about 3 hours, thus very likely ridding themselves of a large part of the heptachlor dose. It was concluded that other methods than dosage with encapsulated chemicals would be needed for appraisal of field effects of toxicants on woodcocks.

Journal of Wildlife Management↗

Long-term effects of 4-aminopyridine exposure to birds and fish

The avian frightening agent, 4-aminopyridine (4AP), was tested on five avian and two fish species to assess the effects of long-term 4AP exposure to nontarget vertebrates. Adult bobwhites ( Colinus virginianus ), mourning doves ( Zenaida macroura ), and ring-necked pheasants ( Phasianus colchicus ) were fed diets containing 3 percent 4AP-treated cracked corn diluted with various ratios of untreated corn for 7 to 35 days. Minimum dilution ratios that produced more than 50 percent mortality were 1:29 for bobwhites and 1:99 for doves. Mortality caused by 4AP could not be determined for pheasants because of their inability to subsist only on corn during the test periods. LCso's were determined for doves (316 ppm) and coturnix quail ( Coturnix coturnix ) (479 ppm) fed exclusively on uniformly treated laboratory rations for 28 to 40 days. Starlings ( Sturnus vulgaris ) treated by gavage daily for 25 days with 1.78 mg/kg 4AP showed no intoxication symptoms. Mortality in all avian species appeared to be the result of acute poisoning, and no evidence of cumulative toxicity was noted in species fed uniformly-treated rations. In 96-hour static tests, channel catfish ( Ictalurus punctatus ) and bluegill (Lepomis macrochirus) showed increasing sensitivity to 4AP with time in test waters ranging from very soft to very hard and from 12 to 22 C. The 96-hour LC 50 's for both species ranged from 2.43 to 7.56 mg/liter (ppm). Toxicity appeared to decrease with increasing water temperatures but was generally unaffected by water hardness. On the basis of the data presented, and the currently registered application rate for 4AP in agricultural crops (0.34 g/ha), long-term hazards to nontarget wildlife were judged to be minimal.

Colorado↗

Responses of Siberian ferrets to secondary zinc phosphide poisoning

The hazard of operational-type applications of zinc phosphide (Zn 3 P 2 ) on a species closely related to the black-footed ferret ( Mustela nigripes ), was evaluated by feeding 16 Siberian ferrets ( M. eversmanni ) rats that had been killed by consumption of 2% zinc phosphide treated bait or by an oral dose of 40, 80, or 160 mg of Zn 3 P 2 . All ferrets accepted rats and a single emesis by each of 3 ferrets was the only evidence of acute intoxication. All ferrets learned to avoid eating gastrointestinal tracts of the rats. Subacute zinc phosphide toxicity in the ferrets was indicated by significant decreases (18-48%) in hemoglobin, increases of 35-91% in serum iron, and elevated levels of serum globulin, cholesterol, and triglycerides. Hemoglobin/iron, urea nitrogen/creatinine, and albumin/globulin ratios also were altered by the treatments. This study demonstrated that Siberian ferrets, or other species with a sensitive emetic reflex, are afforded a degree of protection from acute zinc phosphide poisoning due to its emetic action. The importance of toxicity associated with possible respiratory, liver, and kidney damage indicated by altered blood chemistries is not known.

Journal of Wildlife Management↗

Diuron, fenuron, monuron, neburon, and TCA mixtures as aquatic herbicides in fish habitats

The substituted urea herbicides were rated according to their effectiveness as aquatic herbicides in this order: diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], monuron [3-(p-chlorophenyl)-1,1-dimethylurea], neburon [1-butyl-3-(3,4-dichlorophenyl)-1-methlyurea] and TCA(trichloroacetic acid) mixtures with them. They showed greatest potential in controlling certain aquatic plants in pre-emergence and early postemergence applications. However, relatively high concentrations were required to control filamentous algae ( Cladophora , Pithophora and Spirogyra ) , chara ( Chara ) , coontail ( Ceratophyllum ) , naiad ( Najas ) , and pondweeds ( Potamogeton ) for periods of time exceeding three months and up to three years. Granular formulations achieved better distribution of herbicides for control of rooted aquatic plants along the margins of lakes and ponds. Wettable powder and liquid emulsifiable concentrates were superior to granular formulations for the control of algae and emergent or floating aquatic plants. Monuron and fenuron were less toxic to fish than were diuron and neburon. The TCA mixtures were somewhat more toxic than the simple ureas. Some species of fish were more sensitive than others and fingerlings more sensitive than adults of the same species. Fish-food organisms were reduced appreciably in plastic enclosures at herbicidal concentrations.

Weeds↗

Ducks Get Sick Too!

When it comes to getting sick, wild waterfowl—which include ducks, geese, and swans—are a lot like people. We are all vulnerable to a wide variety of diseases. Some diseases that affect waterfowl, such as avian botulism, have been recognized for many decades as a major cause of death. Others, such as duck plague, are relative newcomers to the known roster of waterfowl diseases. Unfortunately, the number of waterfowl diseases as well as disease-breeding conditions are on the increase. As human development has expanded and encroached on wetlands, more and more waterfowl have been forced into less and less habitat. The resulting crowding can promote the spread of infectious disease caused by toxicants and other noninfectious agents. Although millions of waterfowl die of disease each year, it is often difficult to "see" the disease process occurring. Sick and dying birds usually seek cover to hide, and predators and scavengers eventually devour most of them. When disease becomes epidemic (a disease epidemic in animals is called an epizootic) and sick and dead birds become too numerous for predators and scavengers to eliminate, the disease process becomes far more noticeable. The diseases described in this booklet are among the most common causes of death in wild waterfowl, and include examples of those cause by bacteria, viruses, parasites, fungi, and toxic substances.

Report↗

Biology in focus: better lives through better science: new hope for acid streams

Across the nation, a toxic pollutant turns clean streams orange, kills fish and plant life, and smells like rotten eggs. The culprit is acid mine drainage, the poisonous water leaking from more than 500,000 abandoned and inactive mines in 32 states. The toxic discharge is a problem for operational mines as well. In the Appalachian coal region, for example, acid mine drainage has degraded more than 8,000 miles of streams and has left some aquatic habitats virtually lifeless.

Fact Sheet↗

Understanding contaminants associated with mineral deposits

Interdisciplinary studies by the U.S. Geological Survey (USGS) have resulted in substantial progress in understanding the processes that control the release of metals and acidic water from inactive mines and mineralized areas, the transport of metals and acidic water to streams, and the fate and effect of metals and acidity on downstream ecosystems. The potential environmental effects associated with abandoned and inactive mines, resulting from the complex interaction of a variety of chemical and physical processes, is an area of study that is important to the USGS Mineral Resources Program. Understanding the processes contributing to the environmental effects of abandoned and inactive mines is also of interest to a wide range of stakeholders, including both those responsible for managing lands with historically mined areas and those responsible for anticipating environmental consequences of future mining operations. The recently completed (2007) USGS project entitled 'Process Studies of Contaminants Associated with Mineral Deposits' focused on abandoned and inactive mines and mineralized areas in the Rocky Mountains of Montana, Colorado, New Mexico, Utah, and Arizona, where there are thousands of abandoned mines. Results from these studies provide new information that advances our understanding of the physical and biogeochemical processes causing the mobilization, transport, reaction, and fate of potentially toxic elements (including aluminum, arsenic, cadmium, copper, iron, lead, and zinc) in mineralized near-surface systems and their effects on aquatic and riparian habitat. These interdisciplinary studies provide the basis for scientific decisionmaking and remedial action by local, State, and Federal agencies charged with minimizing the effects of potentially toxic elements on the environment. Current (2007) USGS research highlights the need to understand (1) the geologic sources of metals and acidity and the geochemical reactions that release them from their sources, (2) the pathways that facilitate transport from those sources, and (3) the processes that control the fate of the elements once released from the sources. Experts in the fields of economic geology, structural geology, mineralogy, geophysics, geochemistry, hydrology, ground-water modeling, microbiology, and toxicology came together for a series of studies that address these relationships on scales ranging from the microscopic to the watershed. This Circular presents results and highlights from the detailed, interdisciplinary studies that include investigations in both mining-affected areas and mineralized but unmined areas. The first section of the Circular describes laboratory and site-scale field investigations that primarily focus on mineralogic and biologic controls on the source and release of metals and acidity from mine-waste rock and hydrothermally altered areas. The second section describes a set of basin- to watershed-scale studies that not only investigate the source and release of metals and acidity but also the transport of these constituents away from the source areas. The third section is a summary of results from postremediation ecosystem monitoring. For more information on these and other project-related studies, please visit the project Web site at http://minerals.cr.usgs.gov/projects/contaminants/index.html. The Web site includes a complete bibliography and detailed descriptions of each interdisciplinary study.

Circular↗

Interdisciplinary science approach for harmful algal blooms (HABs) and algal toxins—A strategic science vision for the U.S. Geological Survey

Executive Summary Algal blooms in water, soils, dusts, and the environment have captured national attention because of concerns associated with exposure to algal toxins for humans and animals. Algal blooms naturally occur in all surface-water types and are important primary producers for aquatic ecosystems. However, excessive algae growth can be associated with many harmful effects ranging from aesthetic to toxicity concerns, so this excessive growth is commonly called a harmful algal bloom (HAB). Ecological imbalances that can lead to excessive algal growth, such as increased nutrient availability to waterbodies from natural and anthropogenic sources, are well documented in scientific literature. On the other hand, fundamental scientific understandings of environmental causes and controls leading to algal toxin production, environmental exposures, and adverse health outcomes for humans and animals could benefit from more attention by U.S. Geological Survey (USGS) scientists. Understanding when, why, and how the toxin is produced by individual algal cells or communities and why the toxin is released to the surrounding waterbody requires fundamental research to determine a toxin’s role, whether it provides competitive advantage or if other potential reasons exist for toxin production and release, such as secretions from otherwise benign biological processes. This research will require groundbreaking scientific discovery about underlying biologic and abiotic (non-living) processes commonly complicated by local variation in land use, microbial species composition, and ecosystem structure of the surrounding watershed. Although underlying processes by which HABs form may be similar from one waterbody to another, individual waterbodies may be controlled by local factors for HAB development and toxin production that are unique to the watershed. Consequently, many fundamental science gaps exist that prevent informed mitigation and prevention of toxic HAB events. There are also gaps in understanding local conditions that control algal growth unique to specific watersheds. Addressing these science gaps is needed to inform evidence-based decisions that protect human and animal health and that reduce recreational and socioeconomic losses.

Circular↗

Water-quality indices for specific water uses

Water-quality indices were developed to assess waters for two specific uses--public water supply and irrigation. The assessment for a spcific water use is based on the availability f (of (1) a set of limits for each water quality property selected, (2) a rationale for selection, and (3) information that permits one to appraise the relationship of the concentration of the selected property to the suitability of the specific water use. The selected properties are divided into two classes: Type-I properties, those normaly considered toxic at low concentrations, and type-II properties, those which affect aesthetic conditions or which at high concentrations can be considered toxic or would otherwise render the water unfit for its intended use. (Woodard-USGS)

Circular↗

The handling, hazards, and maintenance of heavy liquids in the geologic laboratory

In geologic laboratories the organic heavy liquids bromoform, methylene iodide, tetrabromoethane, and clerici compounds have been used for years in mineral separation processes. Because the volume of use of these compounds is low, insufficient data is available on their toxic properties. This report is an attempt to summarize the known data from published and industry sources. The physical properties, hazards of handling,proper storage facilities, and adequate protective Clothing are discussed for each compound as well as for their common and less-common solvents. Toxicity data for these materials is listed along with exposure symptoms and suggested first aid treatments. Safety for the worker is emphasized. Three reclamation methods which recover the solvent used as a dilutant and purify the heavy liquid are discussed and illustrated. These include: the water cascade, re fluxing-distillation-condensation, and flash evaporation methods. Various techniques for restoration and stabilization of these heavy liquids are also included.

Circular↗

Water Quality and Algal Data for the North Umpqua River Basin, Oregon, 2005

The upper North Umpqua River Basin has experienced a variety of water-quality problems since at least the early 1990's. Several reaches of the North Umpqua River are listed as water-quality limited under section 303(d) of the Clean Water Act. Diamond Lake, a eutrophic lake that is an important source of water and nutrients to the upper North Umpqua River, is also listed as a water-quality limited waterbody (pH, nuisance algae). A draft Total Maximum Daily Load (TMDL) was proposed for various parameters and is expected to be adopted in full in 2006. Diamond Lake has supported potentially toxic blue-green algae blooms since 2001 that have resulted in closures to recreational water contact and impacts to the local economy. Increased populations of the invasive tui chub fish are reportedly responsible, because they feed on zooplankton that would otherwise control the algal blooms. The Final Environmental Impact Statement (FEIS) for the Diamond Lake Restoration Project advocates reduced fish biomass in Diamond Lake in 2006 as the preferred alternative. A restoration project scheduled to reduce fish biomass for the lake includes a significant water-level drawdown that began in January 2006. After the drawdown of Diamond Lake, the fish toxicant rotenone was applied to eradicate the tui chub. The lake will be refilled and restocked with game fish in 2007. Winter exports of nutrients from Diamond Lake during the restoration project could affect the summer trophic status of the North Umpqua River if retention and recycling in Lemolo Lake are significant. The FEIS includes comprehensive monitoring to assess the water quality of the restored Diamond Lake and the effects of that restoration downstream. One component of the monitoring is the collection of baseline data, in order to observe changes in the river's water quality and algal conditions resulting from the restoration of Diamond Lake. During July 2005, the USGS, in cooperation with Douglas County, performed a synoptic survey of water quality and algal conditions, the results of which can be used for comparison with post-restoration conditions in the river as well as with those documented in an earlier study in 1995. This report presents data from that survey.

Oregon↗

Estuarine bed-sediment-quality data collected in New Jersey and New York after Hurricane Sandy, 2013

This report describes a reconnaissance study of estuarine bed-sediment quality conducted June–October 2013 in New Jersey and New York after Hurricane Sandy in October 2012 to assess the extent of contamination and the potential long-term human and ecological impacts of the storm. The study, funded through the Disaster Relief Appropriations Act of 2013 (PL 113-2), was conducted by the U.S. Geological Survey in cooperation with the U.S. Environmental Protection Agency and the National Oceanographic and Atmospheric Administration. In addition to presenting the bed-sediment-quality data, the report describes the study design, documents the methods of sample collection and analysis, and discusses the steps taken to assure the quality of the data. Bed-sediment samples were collected from June to October 2013 from 167 estuarine sites extending from Cape May, New Jersey, to the New York Harbor and the eastern end of Long Island. Each sampling location and study region was characterized by using geographic information to identify potential contaminant sources. Characterizations included land cover, locations and types of businesses (industrial, financial, and others), spills (sewage, chemical, and others), bulk storage facilities, effluent discharges within 2 kilometers of the sampling point, and discharges within inundated and non-inundated regions near the sampling location. Samples were analyzed for particle size, total organic carbon, metals and trace elements, semivolatile organic compounds, wastewater compounds, hormones, and sediment toxicity. Samples were also screened using x-ray fluorescence, Fourier transform infrared spectroscopy, and x-ray diffraction. In addition, bioassays for endocrine disruptors and protein phosphatase 2A inhibition were conducted. The study was designed to provide the data needed to understand the extent and sources of contamination resulting from Hurricane Sandy, to compare the chemistry and toxicity of estuarine bed sediments before and after the storm, and to evaluate the usefulness of rapid screening and bioassay approaches in disaster settings.

New Jersey, New York↗